CN103035904A - 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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- CN103035904A CN103035904A CN2012105629186A CN201210562918A CN103035904A CN 103035904 A CN103035904 A CN 103035904A CN 2012105629186 A CN2012105629186 A CN 2012105629186A CN 201210562918 A CN201210562918 A CN 201210562918A CN 103035904 A CN103035904 A CN 103035904A
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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 the LiMn2O4 of finding spinel structure can be used as anode material for lithium-ion batteries, since the abundant raw material of its good electrochemistry performance ﹑ come source ﹑ pacify preferably full property can the ﹑ environment-protecting asepsis etc. characteristics become that research is the most active, the exploitation dynamics maximum, one of the positive electrode of tool application prospect, be subject to the favor of vast scientific research institution and commercial company.People tentatively realize the commercialization production of spinel lithium manganate now, are also necessarily used in electric bicycle and electric automobile as the lithium-ion-power cell of positive electrode with it.
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, is fit to large-scale production, but the common mixing of reactant is inhomogeneous, and the synthetic material particle is larger, occurs easily impurity in preparation process, and these shortcomings cause material property relatively poor, and batch stability can not be guaranteed; Microwave process for synthesizing also is a kind of solid phase method synthetic 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, the Gel heat-treatment temperature is low, the powder granule particle diameter is little and narrowly distributing, the powder sintering performance is good, course of reaction is easy to control, equipment is simple, but dry shrink large, the suitability for industrialized production difficulty is large, synthesis cycle is long; The spray process more complicated is unfavorable for industrialization.
The standby LiMn2O4 of Direct Hydrothermal legal system has larger capacity usually, and relatively poor in the cycle performance 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) growth of the LiMn2O4 crystal face of Hydrothermal Synthesis is imperfect, and defective is more; (3) understand the content that reduce active material owing to the loss of manganese in manganate cathode material for lithium and the electrolyte contact process; (4) manganate cathode material for lithium can cause the structure dilation because of the Jahn-Teller effect in charge and discharge process, impact stability.Therefore, people can carry out element doping or surface modification usually in preparation process, to keep higher volumetric properties, improve simultaneously cyclical stability.Because the capacity of LiMn2O4 itself is not high, if whole doping can cause the further decline of capacity, and simple surface modification is can be owing to adhesion weak or seal the lithium ion diffusion admittance and affect material property.
(3) summary of the invention:
First purpose of the present invention provides a kind of modified lithium manganate material LiMn
2-xM
xO
4-δ@LiMn
2O
4, high, the large electric current of this modified lithium manganate material specific capacity and cycle performance are good, stripping that again can establishment manganese and the change in volume that causes because of the Jahn-Teller effect.
Second purpose of the present invention provides the method for a kind of technique simple possible, the described modified lithium manganate material of preparation with low cost.
The 3rd purpose of the present invention is with the positive electrode of described modified lithium manganate material as lithium ion battery.
The below does technical scheme of the present invention and specifies.
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 nuclear, with LiMn
2-xM
xO
4-δNucleocapsid structure for coating layer; Wherein M is a kind of among Al, Ti, Ce, Co, the Ni, and the value of x is that 0.05 ~ 0.5, δ is 0.01 ~ 0.1.
Further, the LiMn of core
2O
4Be the 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 can effectively promote the chemical valence of active material particle surface manganese, suppress the change in volume that causes because of the Jahn-Teller effect in the charge and discharge process, reduce simultaneously possible that the LiMn2O4 core contact with electrolyte, the stripping of minimizing manganese.
The present invention also provides a kind of method for preparing described modified lithium manganate material, adopting relatively inexpensive manganese dioxide is main manganese source, take lithium hydroxide as coprecipitator with the lithium source, mode by manganese ion, other metal ion (M=Al, Ti, Ce, Co, Ni etc.) co-precipitation forms the hybrid packet coating on the manganese dioxide surface, then generates LiMn through hydro-thermal reaction
2-xM
xO
4-δ@LiMn
2O
4Nucleocapsid structure (being called presoma), the crystal face of presoma is reached full growth through subsequent heat treatment again, reduce crystal defect, and keep 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 mixed solution, stir, get lithium hydroxide solution and be added dropwise in the mixed system, make hydroxide coating layer (MnM) OH that forms manganese ion and M metal ion on the manganese dioxide surface; Take the integral molar quantity of manganese ion, M metal ion and manganese dioxide as 100%, wherein the 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 equates with the total mole number of manganese ion, M metal ion and manganese dioxide;
(2) reaction system with step (1) places hydrothermal reaction kettle, in 150 ~ 220
o C reaction 10 ~ 20 hours obtains presoma;
(3) place air atmosphere in 600 ~ 800 presoma
oC high-temperature roasting 2 ~ 5 hours makes described modified lithium manganate material.
Manganese ion of the present invention source is one or more the combination in manganese nitrate, manganese oxalate, manganese acetate, the manganese sulfate.
The combination of one or more in the nitrate that M metal ion source of the present invention is the M metal ion, oxalates, chloride, acetate, the sulfate.
In the described step (1), the mol ratio of manganese ion and M metal ion is 3 ~ 9.
The present invention also provides 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 makes of the present invention
2-xM
xO
4-δ@LiMn
2O
4, its special nucleocapsid structure can be kept the volumetric properties of LiMn2O4, stripping that again can establishment manganese and the change in volume that causes because of the Jahn-Teller effect.
(2) the present invention adopts the mode of co-precipitation coating-hydro-thermal reaction-high-temperature heat treatment to prepare modified lithium manganate material LiMn
2-xM
xO
4-δ@LiMn
2O
4, this technique simple possible, material composition and proportioning are controlled easily, good stability between batch, and with low cost, synthetic lithium manganate material specific capacity is high, and large electric current and cycle performance are good, are expected to be applied in the electrokinetic cell field.
(4) description of drawings
Fig. 1 presses the prepared LiMn of embodiment 1
2-xM
xO
4-δ@LiMn
2O
4X-ray diffraction pattern;
Fig. 2 presses the prepared LiMn of embodiment 1
2-xM
xO
4-δ@LiMn
2O
4Stereoscan photograph;
Fig. 3 presses the prepared LiMn of embodiment 1
2-xM
xO
4-δ@LiMn
2O
4Electron probe micro-analysis figure;
Fig. 4 presses the prepared LiMn of embodiment 1
2-xM
xO
4-δ@LiMn
2O
4Be positive pole, the lithium sheet is the cycle characteristics curve chart of the lithium ion battery that assembles of negative pole;
Fig. 5 building-up process schematic diagram of the present invention.
(5) embodiment
The below is described further technical scheme of the present invention with specific embodiment, but protection scope of the present invention is not limited to this:
Embodiment 1:
Take by weighing ANN aluminium nitrate nonahydrate powder 0.188g, be made into 20ml solution, measure 50wt.% manganese nitrate (Mn (NO
3)
2) solution 0.349ml, splash in the aluminum nitrate solution, stir.Take by weighing 0.696g manganese dioxide, insert mixed liquor, after stirring, take by weighing 0.42g one hydronium(ion) oxidation lithium, be dissolved in the 10ml deionized water, slowly splash in the mixed liquor, stirred 30 minutes.Place hydrothermal reaction kettle with 200 above-mentioned mixed liquor
oC reaction 20 hours, the dry finished product presoma that obtains of filtration washing was through 3 hours 750
oC heat treatment makes LiMn
1.5Al
0.5O
3.95The LiMn that evenly coats
2O
4Powder, the metering of coating layer element chemistry is than being determined by x-ray photoelectron power spectrum (XPS).
To having done the X-ray diffraction analysis with the standby modified lithium manganate material of this legal system, as shown in Figure 1, prepared LiMn2O4 is spinel-type cubic system pure phase structure, does not have the peak of other impurity in the spectrogram.Fig. 2 is LiMn
1.5M
0.5O
4-δ@LiMn
2O
4Powder amplifies 30000 times stereoscan photograph, and as seen from the figure, the 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.
With active material LiMn
1.5M
0.5O
3.95@LiMn
2O
4Powder, acetylene black, Kynoar take by weighing altogether 0.5g and are dissolved in 1-methyl-2 pyrrolidones with the mass ratio of 8:1:1, are applied to after mixing and make positive plate on the aluminium foil.The electrode slice of oven dry is beaten behind the sheet accurately its quality of weighing, as anode.Simultaneously take the lithium sheet as to electrode, the micropore shaped polyethylene is barrier film, 1.0mol/L LiPF
6+ DMC is electrolyte, is assembled into 2032 button cells with tablet press machine in being full of the System One glove box of argon gas.
In 3.3V ~ 4.3V voltage range, battery is carried out the constant current charge-discharge loop test.Fig. 4 is with 1C(130mAg
-1) the 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, the advantage that specific capacity is high under large electric current.
Embodiment 2:
Take by weighing Nickelous nitrate hexahydrate powder 0.145g, be made into 20ml solution, measure 50wt.% manganese nitrate (Mn (NO
3)
2) solution 0.349ml, splash in the nickel nitrate solution, stir.Take by weighing 0.696g manganese dioxide, insert mixed liquor, after stirring, take by weighing 0.42g one hydronium(ion) oxidation lithium, be dissolved in the 10ml deionized water, slowly splash in the mixed liquor, stirred 30 minutes.Place hydrothermal reaction kettle with 200 above-mentioned mixed liquor
oC reaction 20 hours, the dry finished product presoma that obtains of filtration washing was through 3 hours 750
oC heat treatment makes LiMn
1.5Ni
0.5O
3.95The LiMn that evenly coats
2O
4Powder, the metering of coating layer element chemistry is than being determined by x-ray photoelectron power spectrum (XPS).
Take the modified lithium manganate material that makes as positive electrode, be assembled into 2032 button cells according to the method for embodiment 1, in 3.3V ~ 4.3V voltage range, battery is carried out the constant current charge-discharge loop test, with 1C(130mAg
-1) the multiplying power charging, it is at 1C(130mAg
-1) and 10C(1300mAg
-1) first discharge capacity and 50 all capability retentions of multiplying power discharging see Table 1.
Embodiment 3:
Take by weighing six nitric hydrate cerium powder 0.217g, be made into 20ml solution, measure 50wt.% manganese nitrate (Mn (NO
3)
2) solution 0.349ml, splash in the cerous nitrate solution, stir.Take by weighing 0.696g manganese dioxide, insert mixed liquor, after stirring, take by weighing 0.42g one hydronium(ion) oxidation lithium, be dissolved in the 10ml deionized water, slowly splash in the mixed liquor, stirred 30 minutes.Place hydrothermal reaction kettle with 200 above-mentioned mixed liquor
oC reaction 20 hours, the dry finished product presoma that obtains of filtration washing was through 3 hours 750
oC heat treatment makes LiMn
1.5Ce
0.5O
3.97The LiMn that evenly coats
2O
4Powder, the metering of coating layer element chemistry is than being determined by x-ray photoelectron power spectrum (XPS).
Take the modified lithium manganate material that makes as positive electrode, be assembled into 2032 button cells according to the method for embodiment 1, in 3.3V ~ 4.3V voltage range, battery is carried out the constant current charge-discharge loop test, with 1C(130mAg
-1) the multiplying power charging, it is at 1C(130mAg
-1) and 10C(1300mAg
-1) first discharge capacity and 50 all capability retentions of multiplying power discharging see Table 1.
Embodiment 4:
Take by weighing cabaltous nitrate hexahydrate powder 0.146g, be made into 20ml solution, measure 50wt.% manganese nitrate (Mn (NO
3)
2) solution 0.349ml, splash in the cobalt nitrate solution, stir.Take by weighing 0.696g manganese dioxide, insert mixed liquor, after stirring, take by weighing 0.42g one hydronium(ion) oxidation lithium, be dissolved in the 10ml deionized water, slowly splash in the mixed liquor, stirred 30 minutes.Place hydrothermal reaction kettle with 200 above-mentioned mixed liquor
oC reaction 20 hours, the dry finished product presoma that obtains of filtration washing was through 3 hours 750
oC heat treatment makes LiMn
1.5Co
0.5O
3.95The LiMn that evenly coats
2O
4Powder, the metering of coating layer element chemistry is than being determined by x-ray photoelectron power spectrum (XPS).
Take the modified lithium manganate material that makes as positive electrode, be assembled into 2032 button cells according to the method for embodiment 1, in 3.3V ~ 4.3V voltage range, battery is carried out the constant current charge-discharge loop test, with 1C(130mAg
-1) the multiplying power charging, it is at 1C(130mAg
-1) and 10C(1300mAg
-1) first discharge capacity and 50 all capability retentions of multiplying power discharging see Table 1.
Embodiment 5:
Take by weighing ANN aluminium nitrate nonahydrate powder 0.376g, be made into 20ml solution, measure 50% manganese nitrate (Mn (NO
3)
2) solution 2.094ml, splash in the aluminum nitrate solution, after stirring, take by weighing 0.42g one hydronium(ion) oxidation lithium, be dissolved in the 10ml deionized water, slowly splash in the mixed liquor, stirred 30 minutes.Place hydrothermal reaction kettle with 200 above-mentioned mixed liquor
oC reaction 20 hours, the dry finished product presoma that obtains of filtration washing was through 3 hours 750
oC heat treatment makes LiMn
1.8Al
0.2O
3.98Powder.
With the LiMn that makes
1.8Al
0.2O
3.98Be positive electrode, be assembled into 2032 button cells according to the method for embodiment 1, in 3.3V ~ 4.3V voltage range, battery is carried out the constant current charge-discharge loop test, with 1C(130mAg
-1) the multiplying power charging, it is at 1C(130mAg
-1) and 10C(1300mAg
-1) first discharge capacity and 50 all capability retentions of multiplying power discharging see Table 1.
Embodiment 6:
Take by weighing 0.87g manganese dioxide and 0.42g one hydronium(ion) oxidation lithium, be dissolved in the 30ml deionized water, stirred 30 minutes.Place hydrothermal reaction kettle with 200 above-mentioned mixed liquor
oC reaction 20 hours, the dry finished product LiMn that obtains of filtration washing
2O
4Powder.
With the LiMn that makes
2O
4Be positive electrode, be assembled into 2032 button cells according to the method for embodiment 1, in 3.3V ~ 4.3V voltage range, battery is carried out the constant current charge-discharge loop test, with 1C(130mAg
-1) the multiplying power charging, it is at 1C(130mAg
-1) and 10C(1300mAg
-1) first discharge capacity and 50 all capability retentions of multiplying power discharging see Table 1.
Embodiment 7:
Take by weighing six nitric hydrate cerium powder 0.217g, be made into 20ml solution, measure 50% manganese nitrate (Mn (NO
3)
2) solution 0.349ml, splash in the cerous nitrate solution, stir.Take by weighing 0.696g manganese dioxide, insert mixed liquor, after stirring, take by weighing 0.42g one hydronium(ion) oxidation lithium, be dissolved in the 10ml deionized water, slowly splash in the mixed liquor, stirred 30 minutes.Place hydrothermal reaction kettle with 220 above-mentioned mixed liquor
oC reaction 15 hours, the dry finished product presoma that obtains of filtration washing was through 3 hours 750
oC heat treatment makes LiMn
1.5Ce
0.5O
3.97The LiMn that evenly coats
2O
4Powder, the metering of coating layer element chemistry is than being determined by x-ray photoelectron power spectrum (XPS).
With the LiMn that makes
1.5Ce
0.5O
3.97The LiMn that evenly coats
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, battery is carried out the constant current charge-discharge loop test, with 1C(130mAg
-1) the multiplying power charging, it is at 1C(130mAg
-1) and 10C(1300mAg
-1) first discharge capacity and 50 all capability retentions of multiplying power discharging see Table 1.
Embodiment 8:
Take by weighing six nitric hydrate cerium powder 0.217g, be made into 20ml solution, measure 50% manganese nitrate (Mn (NO3) 2) solution 0.349ml, splash in the cerous nitrate solution, stir.Take by weighing 0.696g manganese dioxide, insert mixed liquor, after stirring, take by weighing 0.42g one hydronium(ion) oxidation lithium, be dissolved in the 10ml deionized water, slowly splash in the mixed liquor, stirred 30 minutes.Place hydrothermal reaction kettle with 200 above-mentioned mixed liquor
oC reaction 20 hours, the dry finished product presoma that obtains of filtration washing was through 3 hours 650
oC heat treatment makes LiMn
1.5Ce
0.5O
3.97The LiMn that evenly coats
2O
4Powder, the metering of coating layer element chemistry is than being determined by x-ray photoelectron power spectrum (XPS).
With the LiMn that makes
1.5Ce
0.5O
3.97The LiMn that evenly coats
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, battery is carried out the constant current charge-discharge loop test, with 1C(130mAg
-1) the multiplying power charging, it is at 1C(130mAg
-1) and 10C(1300mAg
-1) first discharge capacity and 50 all capability retentions of multiplying power discharging see Table 1.
Embodiment 9:
Take by weighing six nitric hydrate cerium powder 0.130g, be made into 20ml solution, measure 50% manganese nitrate (Mn (NO
3)
2) solution 0.396ml, splash in the cerous nitrate solution, stir.Take by weighing 0.696g manganese dioxide, insert mixed liquor, after stirring, take by weighing 0.42g one hydronium(ion) oxidation lithium, be dissolved in the 10ml deionized water, slowly splash in the mixed liquor, stirred 30 minutes.Place hydrothermal reaction kettle with 200 above-mentioned mixed liquor
oC reaction 20 hours, the dry finished product presoma that obtains of filtration washing was through 3 hours 750
oC heat treatment makes LiMn
1.7Ce
0.3O
3.96The LiMn that evenly coats
2O
4Powder, the metering of coating layer element chemistry is than being determined by x-ray photoelectron power spectrum (XPS).
With the LiMn that makes
1.7Ce
0.3O
3.96The LiMn that evenly coats
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, battery is carried out the constant current charge-discharge loop test, with 1C(130mAg
-1) the multiplying power charging, it is at 1C(130mAg
-1) and 10C(1300mAg
-1) first discharge capacity and 50 all capability retentions of multiplying power discharging see Table 1.
Embodiment 10:
Take by weighing ANN aluminium nitrate nonahydrate powder 0.188g, be made into 20ml solution, measure 50% manganese nitrate (Mn (NO
3)
2) solution 0.349ml, splash in the aluminum nitrate solution, stir.Take by weighing 0.696g manganese dioxide, insert mixed liquor, after stirring, take by weighing 0.42g one hydronium(ion) oxidation lithium, be dissolved in the 10ml deionized water, slowly splash in the mixed liquor, stirred 30 minutes.Place hydrothermal reaction kettle with 220 above-mentioned mixed liquor
oC reaction 15 hours, the dry finished product presoma that obtains of filtration washing was through 3 hours 750
oC heat treatment makes LiMn
1.5Al
0.5O
3.95The LiMn that evenly coats
2O
4Powder, the metering of coating layer element chemistry is than being determined by x-ray photoelectron power spectrum (XPS).
With the LiMn that makes
1.5Al
0.5O
3.95The LiMn that evenly coats
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, battery is carried out the constant current charge-discharge loop test, with 1C(130mAg
-1) the multiplying power charging, it is at 1C(130mAg
-1) and 10C(1300mAg
-1) first discharge capacity and 50 all capability retentions of multiplying power discharging see Table 1.
Embodiment 11:
Take by weighing ANN aluminium nitrate nonahydrate powder 0.188g, be made into 20ml solution, measure 50% manganese nitrate (Mn (NO
3)
2) solution 0.349ml, splash in the aluminum nitrate solution, stir.Take by weighing 0.696g manganese dioxide, insert mixed liquor, after stirring, take by weighing 0.42g one hydronium(ion) oxidation lithium, be dissolved in the 10ml deionized water, slowly splash in the mixed liquor, stirred 30 minutes.Place hydrothermal reaction kettle with 200 above-mentioned mixed liquor
oC reaction 20 hours, the dry finished product presoma that obtains of filtration washing was through 3 hours 650
oC heat treatment makes LiMn
1.5Al
0.5O
3.95The LiMn that evenly coats
2O
4Powder, the metering of coating layer element chemistry is than being determined by x-ray photoelectron power spectrum (XPS).
With the LiMn that makes
1.5Al
0.5O
3.95The LiMn that evenly coats
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, battery is carried out the constant current charge-discharge loop test, with 1C(130mAg
-1) the multiplying power charging, it is at 1C(130mAg
-1) and 10C(1300mAg
-1) first discharge capacity and 50 all capability retentions of multiplying power discharging see Table 1.
Embodiment 12:
Take by weighing ANN aluminium nitrate nonahydrate powder 0.113g, be made into 20ml solution, measure 50% manganese nitrate (Mn (NO
3)
2) solution 0.396ml, splash in the aluminum nitrate solution, stir.Take by weighing 0.696g manganese dioxide, insert mixed liquor, after stirring, take by weighing 0.42g one hydronium(ion) oxidation lithium, be dissolved in the 10ml deionized water, slowly splash in the mixed liquor, stirred 30 minutes.Place hydrothermal reaction kettle with 200 above-mentioned mixed liquor
oC reaction 20 hours, the dry finished product presoma that obtains of filtration washing was through 3 hours 750
oC heat treatment makes LiMn
1.7Al
0.3O
3.95The LiMn that evenly coats
2O
4Powder, the metering of coating layer element chemistry is than being determined by x-ray photoelectron power spectrum (XPS).
With the LiMn that makes
1.7Al
0.3O
3.95The LiMn that evenly coats
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, battery is carried out the constant current charge-discharge loop test, with 1C(130mAg
-1) the multiplying power charging, it is at 1C(130mAg
-1) and 10C(1300mAg
-1) first discharge capacity and 50 all capability retentions of multiplying power discharging see Table 1.
Table 1: with the prepared LiMn of embodiment 1 ~ 12
2-xM
xO
4-δ@LiMn
2O
4Be positive pole, the lithium sheet is that the lithium ion battery chemical property that negative pole assembles compares
Claims (8)
1. modified lithium manganate material, it is characterized in that: described modified lithium manganate material is with LiMn
2O
4For nuclear, with LiMn
2-xM
xO
4-δNucleocapsid structure for coating layer; Wherein M is a kind of among Al, Ti, Ce, Co, the Ni, and the value of x is that 0.05 ~ 0.5, δ is 0.01 ~ 0.1.
2. modified lithium manganate material as claimed in claim 1 is characterized in that: described LiMn
2O
4It is the spinel-type cubic crystal structure.
3. modified lithium manganate material as claimed in claim 1, it is characterized in that: the particle diameter of described modified lithium manganate material is at 100 ~ 500 nm.
4. modified lithium manganate material as claimed in claim 1, it is characterized in that: the value of x is that 0.2 ~ 0.5, δ is 0.02 ~ 0.06.
5. modified lithium manganate material preparation method as claimed in claim 1, it is characterized in that: described preparation method comprises the steps:
(1) manganese ion Yuan ﹑ M metal ion source is mixed with mixed solution, then manganese dioxide is placed mixed solution, stir, get lithium hydroxide solution and be added dropwise in the mixed system, make hydroxide coating layer (MnM) OH that forms manganese ion and M metal ion on the manganese dioxide surface; Take the integral molar quantity of manganese ion, M metal ion and manganese dioxide as 100%, wherein the 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 equates with the total mole number of manganese ion, M metal ion and manganese dioxide;
(2) reaction system with step (1) places hydrothermal reaction kettle, in 150 ~ 220
oC reaction 10 ~ 20 hours obtains presoma;
(3) place air atmosphere in 600 ~ 800 presoma
oC high-temperature roasting 2 ~ 5 hours makes described modified lithium manganate material.
6. preparation method according to claim 5, it is characterized in that: described manganese ion source is one or more the combination in manganese nitrate, manganese oxalate, manganese acetate, the manganese sulfate, the combination of one or more in the nitrate that described M metal ion source is the M metal ion, oxalates, chloride, acetate, the sulfate.
7. preparation method according to claim 5, it is characterized in that: in the described step (1), the mol ratio that makes manganese ion and M metal ion is 3 ~ 9.
8. modified lithium manganate material as claimed in claim 1 is as the application of the positive electrode of lithium ion battery.
Priority Applications (1)
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| CN111509224A (en) * | 2020-04-17 | 2020-08-07 | 中南大学 | Linked modified lithium-rich manganese-based cathode material and preparation method thereof |
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| CN109728375A (en) * | 2017-10-30 | 2019-05-07 | 微宏动力系统（湖州）有限公司 | A kind of positive electrode and lithium ion battery recycled and repair the method for positive electrode, reparation |
| CN111509224A (en) * | 2020-04-17 | 2020-08-07 | 中南大学 | Linked modified lithium-rich manganese-based cathode material and preparation method thereof |
| CN111509224B (en) * | 2020-04-17 | 2021-07-23 | 中南大学 | Linked modified lithium-rich manganese-based cathode material and preparation method thereof |
| CN114464793A (en) * | 2022-02-11 | 2022-05-10 | 湖北亿纬动力有限公司 | Composite cathode material, preparation method thereof and lithium ion battery |
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