CN104157844B - High-rate lithium-rich manganese-based anode material of a kind of nano-micro structure and preparation method thereof - Google Patents
High-rate lithium-rich manganese-based anode material of a kind of nano-micro structure and preparation method thereof Download PDFInfo
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Abstract
High-rate lithium-rich manganese-based anode material of a kind of nano-micro structure and preparation method thereof, belongs to field of material synthesis technology.The chemical formula of described positive electrode is aLi
2mnO
3(1-a) LiMO
2, wherein 0.3≤a < 1, M=Ni
xco
ymn
1-x-y, 0≤x≤0.5,0≤y≤0.5.Preparation method is: one, take manganese salt, surfactant and sodium chlorate Homogeneous phase mixing, carries out the radial hollow nano-micro structure that hydro-thermal reaction obtains being formed by manganese dioxide nano-rod self assembly; The manganese dioxide of the nano-micro structure two, step one obtained and lithium salts, cobalt salt and nickel salt Homogeneous phase mixing obtain presoma; Three, by presoma high-temperature calcination, the lithium-rich manganese-based anode material with nano-micro structure is obtained.The present invention has by utilizing the advantage that in nano-micro structure, nanostructure intrinsic carrier the evolving path is short, effectively can improve the rate capability of material, also can utilize the characteristics such as the low not easily reunion of micrometer structure surface energy, chemical stability height simultaneously, keep the cycle performance of material.
Description
Technical field
The invention belongs to field of material synthesis technology, relate to a kind of anode material for lithium-ion batteries and preparation method thereof, high-rate lithium-rich manganese-based anode material particularly relating to a kind of nano-micro structure and preparation method thereof.
Background technology
Lithium ion battery is the battery system that in current secondary cell system, energy density is the highest, there is the remarkable advantages such as memory-less effect, operating voltage is high, self-discharge rate is little, it is used widely in field of portable electronic apparatus, has also shown huge application prospect in the field such as electric automobile and energy-accumulating power station simultaneously.
For existing positive electrode, LiCoO
2due to during deep charge to electrolytical strong oxidation and excessively de-lithium to the destruction of self structure, about its actual active volume only has the half of theoretical capacity.LiCoO is substituted with Mn and/or Ni
2in Co (typical in LiNi
1/3co
1/3mn
1/3o
2and LiNi
1/2mn
1/2o
2although) reduce material cost and toxicity, significantly improve the fail safe of material, the actual specific capacity (being generally less than 180mAh/g) of these layer structure materials does not have large breakthrough; Spinel structure positive electrode LiMn
2o
4with polyanion positive electrode (typically as the LiFePO of olivine structural
4) theoretical specific capacity also only have 148mAh/g and 170mAh/g respectively, far can not meet the performance requirement of high specific energy lithium ion battery to positive electrode.Therefore, positive electrode becomes the bottleneck that performance of lithium ion battery improves further.Compared with above-mentioned several positive electrode, the theoretical capacity of stratiform lithium-rich manganese base material can more than 250mAh/g, by one of important candidate's positive electrode becoming lithium ion battery of future generation.But lithium-rich manganese-based anode material conductivity is on the low side, heavy-current discharge and high rate capability poor, in cyclic process, capacity attenuation is fast, and these shortcomings have become the technical bottleneck of restriction lithium-rich manganese-based anode material application.
Summary of the invention
High-rate lithium-rich manganese-based anode material that the object of this invention is to provide a kind of nano-micro structure and preparation method thereof.By utilizing, there is the advantage that in nano-micro structure, nanostructure intrinsic carrier the evolving path is short, effectively can improve the rate capability of material, also can utilize the characteristics such as the low not easily reunion of micrometer structure surface energy, chemical stability height simultaneously, keep the cycle performance of material.
A high-rate lithium-rich manganese-based anode material for nano-micro structure, chemical formula is aLi
2mnO
3(1-a) LiMO
2, wherein 0.3≤a < 1, M=Ni
xco
ymn
1-x-y, 0≤x≤0.5,0≤y≤0.5.
The preparation method of the high-rate lithium-rich manganese-based anode material of above-mentioned nano-micro structure, adopt hydro thermal method to prepare the lithium-rich manganese-based anode material of the radial hollow nano-micro structure that nanometer rods self assembly is formed, concrete preparation method is as follows:
One, 1: 1 ~ 1.5: 3 ~ 5 take manganese salt in molar ratio, surfactant and sodium chlorate, by appropriate amount of deionized water stirring and dissolving to clarification, mixed solution is proceeded in the autoclave of inner liner polytetrafluoroethylene, be placed in the baking oven of 150 ~ 200 DEG C, the control reaction time is 10 ~ 16h, question response still naturally cools to room temperature, filter, obtain black precipitate, with deionized water and ethanol repeatedly clean to pH be 6 ~ 8, be positioned over dry 24 ~ 48h in the baking oven of 80 ~ 120 DEG C, obtain black powder manganese dioxide A, it has the radial hollow nano-micro structure formed by nanometer rods self assembly,
Two, lithium salts, nickel salt, cobalt salt and step one are obtained the manganese dioxide A Homogeneous phase mixing with nano-micro structure, obtain precursor B;
Three, precursor B is put into Muffle furnace air atmosphere, 300 ~ 500 DEG C of pre-burning 3 ~ 8h are risen to from room temperature with 1 ~ 5 DEG C/min heating rate, be warming up to 600 ~ 900 DEG C of calcining 6 ~ 15h with identical heating rate again, obtain the lithium-rich manganese-based anode material with nano-micro structure.
In above-mentioned preparation method, described manganese salt compound is one or more the mixture in manganese sulfate, manganese acetate, manganese oxalate or manganese nitrate.
In above-mentioned preparation method, described surfactant is the one in polyvinylpyrrolidone, DTAB, TTAB, softex kw.
In above-mentioned preparation method, described lithium salt compound is one or more the mixture in lithium hydroxide, lithium acetate, lithium nitrate, lithium ethoxide, lithium formate, lithium carbonate.
In above-mentioned preparation method, described nickel salt compound is one or more the mixture in nickelous sulfate, nickel acetate, nickel oxalate or nickel nitrate.
In above-mentioned preparation method, described cobalt salt compound is one or more the mixture in cobaltous sulfate, cobalt acetate, cobalt oxalate or cobalt nitrate.
In above-mentioned preparation method, described hybrid mode is liquid phase mixing or solid phase mixing.
In above-mentioned preparation method, described calcination atmosphere is air.
In above-mentioned preparation method, it is 10 ~ 20 μm of radial hollow nano-micro structures that described manganese dioxide has the diameter formed by the nanometer rods self assembly of diameter 200 ~ 400nm.
In above-mentioned preparation method, it is 10 ~ 20 μm of radial hollow nano-micro structures that described lithium-rich manganese-based anode material has the diameter formed by the nanometer rods self assembly of diameter 200 ~ 400nm.
The present invention has following beneficial effect:
(1) adopting the lithium-rich manganese-based anode material of this method preparation synthesis to have diameter that is special, that formed by the nanometer rods self assembly of diameter 200 ~ 400nm is 10 ~ 20 μm of radial hollow nano-micro structures.
(2) by utilizing the advantage that in the special nano-micro structure of this lithium-rich manganese-based anode material, nanostructure intrinsic carrier the evolving path is short, effectively can improve the rate capability of material, also can utilize the characteristics such as the low not easily reunion of micrometer structure surface energy, chemical stability height simultaneously, keep the cycle performance of material
(3) present invention process is simple, performance boost is obviously reliable, and the lithium-rich manganese-based anode material of preparation has higher rate capability and excellent cycle performance.
Accompanying drawing explanation
Fig. 1 to be the multiplication factor with the manganese dioxide of nano-micro structure prepared by the present invention be 3000 SEM figure.
Fig. 2 to be the multiplication factor with the manganese dioxide of nano-micro structure prepared by the present invention be 10000 SEM figure.
Fig. 3 to be the multiplication factor with the lithium-rich manganese-based anode material of nano-micro structure prepared by the present invention be 10000 SEM figure.
Fig. 4 is the XRD figure with the lithium-rich manganese-based anode material of nano-micro structure prepared by the embodiment of the present invention 1.
Fig. 5 is the high rate performance curve with the lithium-rich manganese-based anode material button electricity of nano-micro structure prepared by the embodiment of the present invention 1.
Fig. 6 is the cycle performance curve with the lithium-rich manganese-based anode material button electricity of nano-micro structure prepared by the embodiment of the present invention 1.
Embodiment
Below in conjunction with accompanying drawing, technical scheme of the present invention is further described; but be not limited thereto; everyly technical solution of the present invention modified or equivalent to replace, and not departing from the spirit and scope of technical solution of the present invention, all should be encompassed in protection scope of the present invention.
Embodiment 1:
Take manganese sulfate at 1: 1.1: 3 in molar ratio, polyvinylpyrrolidone and sodium chlorate, by appropriate amount of deionized water stirring and dissolving to clarification, mixed solution is proceeded in the autoclave of inner liner polytetrafluoroethylene, be placed in the baking oven of 180 DEG C, the control reaction time is 12h, question response still naturally cools to room temperature, filter, obtain black precipitate, with deionized water and ethanol repeatedly clean to pH be 7, be positioned over dry 48h in the baking oven of 110 DEG C, obtain black manganese dioxide powder has the radial hollow nano-micro structure formed by nanometer rods self assembly, as Fig. 1, shown in 2,
Take lithium hydroxide, nickel acetate, manganese dioxide at Li: Ni: Mn=1.2: 0.2: 0.6 in molar ratio, and in deionized water and alcohol mixed solution Homogeneous phase mixing; Rise to 500 DEG C with 2 DEG C/min heating rate from room temperature, pre-burning 5h, then rise to 750 DEG C with identical heating rate, calcining 10h, obtain the lithium-rich manganese-based anode material with nano-micro structure, chemical formula is 0.5Li
2mnO
30.5LiNi
0.5mn
0.5o
2.
As shown in Figure 3, the lithium-rich manganese-based anode material of prepared by the present embodiment have nano-micro structure has homogeneous nano-micro structure, and concrete manifestation is the diameter 10 μm of radial hollow-core constructions formed by the nanometer rods self assembly of diameter 200nm.As shown in Figure 4, there is superlattice characteristic peak in the XRD curve of prepared by the present embodiment the have lithium-rich manganese-based anode material of nano-micro structure, illustrates that synthetic material is lithium-rich manganese base material.By the lithium-rich manganese-based anode material assembly simulation lithium ion battery with nano-micro structure obtained, in 2 ~ 4.8V interval, carry out electrochemical property test, carry out with 0.05C activation, first discharge specific capacity can reach 261.6mAh/g; High rate performance test is carried out to the lithium-rich manganese-based anode material assembly simulation lithium ion battery with nano-micro structure prepared by the present embodiment, as shown in Figure 5,0.2,0.5,1,2,5, under 10C specific discharge capacity be about 254 respectively, 228,204,182,147,112mAh/g; As shown in Figure 6, carry out 50 circulations under 5C after, specific discharge capacity can reach 141.2mAh/g, and capability retention is 96.1%.
Embodiment 2:
Take manganese nitrate, polyvinylpyrrolidone and sodium chlorate at 1: 1: 4 in molar ratio, by appropriate amount of deionized water stirring and dissolving to clarification, mixed solution is proceeded in the autoclave of inner liner polytetrafluoroethylene, be placed in the baking oven of 200 DEG C, the control reaction time is 10h, question response still naturally cools to room temperature, filter, obtain black precipitate, with deionized water and ethanol repeatedly clean to pH be 7, be positioned over dry 48h in the baking oven of 110 DEG C, obtain black manganese dioxide powder has the radial hollow nano-micro structure formed by nanometer rods self assembly;
Take lithium acetate, cobalt acetate, manganese dioxide at Li: Co: Mn=1.2: 0.2: 0.6 in molar ratio, and in deionized water and alcohol mixed solution Homogeneous phase mixing; Rise to 500 DEG C with 2 DEG C/min heating rate from room temperature, pre-burning 5h, then rise to 750 DEG C with identical heating rate, calcining 8h, obtain the lithium-rich manganese-based anode material with nano-micro structure, chemical formula is 0.5Li
2mnO
30.5LiCo
0.5mn
0.5o
2.
The lithium-rich manganese-based anode material of prepared by the present embodiment have nano-micro structure has homogeneous nano-micro structure, and concrete manifestation is the diameter 15 μm of radial hollow-core constructions formed by the nanometer rods self assembly of diameter 200nm.There is superlattice characteristic peak in the XRD curve of prepared by the present embodiment the have lithium-rich manganese-based anode material of nano-micro structure, illustrates that synthetic material is lithium-rich manganese base material.By the lithium-rich manganese-based anode material assembly simulation lithium ion battery with nano-micro structure obtained, in 2 ~ 4.8V interval, carry out electrochemical property test, carry out with 0.05C activation, first discharge specific capacity can reach 262.5mAh/g; High rate performance test is carried out to the lithium-rich manganese-based anode material assembly simulation lithium ion battery with nano-micro structure prepared by the present embodiment, 0.2,0.5,1,2,5, under 10C specific discharge capacity be about 254 respectively, 233,205,183,151,113mAh/g; Carry out 50 circulations under 5C after, specific discharge capacity can reach 142.5mAh/g, and capability retention is 94.4%.
Embodiment 3:
Take manganese oxalate, softex kw and sodium chlorate at 1: 1: 4 in molar ratio, by appropriate amount of deionized water stirring and dissolving to clarification, mixed solution is proceeded in the autoclave of inner liner polytetrafluoroethylene, be placed in the baking oven of 200 DEG C, the control reaction time is 10h, question response still naturally cools to room temperature, filter, obtain black precipitate, with deionized water and ethanol repeatedly clean to pH be 7, be positioned over dry 48h in the baking oven of 110 DEG C, obtain black manganese dioxide powder has the radial hollow nano-micro structure formed by nanometer rods self assembly;
Take lithium oxalate, nickel oxalate, manganese dioxide at Li: Mn: Ni=1.13: 0.3: 0.57 in molar ratio, and in deionized water and alcohol mixed solution Homogeneous phase mixing; Rise to 500 DEG C with 2 DEG C/min heating rate from room temperature, pre-burning 5h, then rise to 800 DEG C with identical heating rate, calcining 8h, obtain the lithium-rich manganese-based anode material with nano-micro structure, chemical formula is 0.3Li
2mnO
30.7LiNi
0.5mn
0.5o
2.
The lithium-rich manganese-based anode material of prepared by the present embodiment have nano-micro structure has homogeneous nano-micro structure, and concrete manifestation is the diameter 15 μm of radial hollow-core constructions formed by the nanometer rods self assembly of diameter 300nm.There is superlattice characteristic peak in the XRD curve of prepared by the present embodiment the have lithium-rich manganese-based anode material of nano-micro structure, illustrates that synthetic material is lithium-rich manganese base material.By the lithium-rich manganese-based anode material assembly simulation lithium ion battery with nano-micro structure obtained, in 2 ~ 4.8V interval, carry out electrochemical property test, carry out with 0.05C activation, first discharge specific capacity can reach 258.5mAh/g; High rate performance test is carried out to the lithium-rich manganese-based anode material assembly simulation lithium ion battery with nano-micro structure prepared by the present embodiment, 0.2,0.5,1,2,5, under 10C specific discharge capacity be about 252 respectively, 230,198,178,141,108mAh/g; Carry out 50 circulations under 5C after, specific discharge capacity can reach 132.6mAh/g, and capability retention is 94.0%.
Embodiment 4:
Take manganese acetate, TTAB and sodium chlorate at 1: 1.05: 4 in molar ratio, by appropriate amount of deionized water stirring and dissolving to clarification, mixed solution is proceeded in the autoclave of inner liner polytetrafluoroethylene, be placed in the baking oven of 160 DEG C, the control reaction time is 15h, question response still naturally cools to room temperature, filter, obtain black precipitate, with deionized water and ethanol repeatedly clean to pH be 7, be positioned over dry 48h in the baking oven of 110 DEG C, obtain black manganese dioxide powder has the radial hollow nano-micro structure formed by nanometer rods self assembly;
Take lithium acetate, nickel acetate, cobalt acetate, manganese dioxide at Li: Ni: Co: Mn=1.12: 0.26: 0.26: 0.36 in molar ratio, and in deionized water and alcohol mixed solution Homogeneous phase mixing; Rise to 500 DEG C with 3 DEG C/min heating rate from room temperature, pre-burning 5h, then rise to 800 DEG C with identical heating rate, calcining 10h, obtain the lithium-rich manganese-based anode material with nano-micro structure, chemical formula is 0.5Li
2mnO
30.5LiNi
0.5co
0.5o
2.
The lithium-rich manganese-based anode material of prepared by the present embodiment have nano-micro structure has homogeneous nano-micro structure, and concrete manifestation is the diameter 12 μm of radial hollow-core constructions formed by the nanometer rods self assembly of diameter 200nm.There is superlattice characteristic peak in the XRD curve of prepared by the present embodiment the have lithium-rich manganese-based anode material of nano-micro structure, illustrates that synthetic material is lithium-rich manganese base material.By the lithium-rich manganese-based anode material assembly simulation lithium ion battery with nano-micro structure obtained, in 2 ~ 4.8V interval, carry out electrochemical property test, carry out with 0.05C activation, first discharge specific capacity can reach 261.9mAh/g; High rate performance test is carried out to the lithium-rich manganese-based anode material assembly simulation lithium ion battery with nano-micro structure prepared by the present embodiment, 0.2,0.5,1,2,5, under 10C specific discharge capacity be about 257 respectively, 236,206,184,146,116mAh/g; Carry out 50 circulations under 5C after, specific discharge capacity can reach 138.2mAh/g, and capability retention is 94.7%.
Embodiment 5:
Take manganese sulfate, DTAB and sodium chlorate at 1: 1.2: 4 in molar ratio, by appropriate amount of deionized water stirring and dissolving to clarification, mixed solution is proceeded in the autoclave of inner liner polytetrafluoroethylene, be placed in the baking oven of 200 DEG C, the control reaction time is 12h, question response still naturally cools to room temperature, filter, obtain black precipitate, with deionized water and ethanol repeatedly clean to pH be 7, be positioned over dry 48h in the baking oven of 110 DEG C, obtain black manganese dioxide powder has the radial hollow nano-micro structure formed by nanometer rods self assembly;
Take lithium acetate, nickel acetate, cobalt acetate, manganese dioxide at Li: Ni: Co: Mn=1.2: 0.136: 0.36: 0.528 in molar ratio, and in deionized water and alcohol mixed solution Homogeneous phase mixing; Rise to 500 DEG C with 3 DEG C/min heating rate from room temperature, pre-burning 5h, then rise to 800 DEG C with identical heating rate, calcining 10h, obtain the lithium-rich manganese-based anode material with nano-micro structure, chemical formula is 0.5Li
2mnO
30.5LiNi
1/3ni
1/3mn
1/3o
2.
The lithium-rich manganese-based anode material of prepared by the present embodiment have nano-micro structure has homogeneous nano-micro structure, and concrete manifestation is the diameter 15 μm of radial hollow-core constructions formed by the nanometer rods self assembly of diameter 200nm.There is superlattice characteristic peak in the XRD curve of prepared by the present embodiment the have lithium-rich manganese-based anode material of nano-micro structure, illustrates that synthetic material is lithium-rich manganese base material.By the lithium-rich manganese-based anode material assembly simulation lithium ion battery with nano-micro structure obtained, in 2 ~ 4.8V interval, carry out electrochemical property test, carry out with 0.05C activation, first discharge specific capacity can reach 262.1mAh/g; High rate performance test is carried out to the lithium-rich manganese-based anode material assembly simulation lithium ion battery with nano-micro structure prepared by the present embodiment, 0.2,0.5,1,2,5, under 10C specific discharge capacity be about 253 respectively, 232,204,186,145,111mAh/g; Carry out 50 circulations under 5C after, specific discharge capacity can reach 139.6mAh/g, and capability retention is 96.3%.
Embodiment 6:
Take manganese nitrate, polyvinylpyrrolidone and sodium chlorate at 1: 1.1: 4 in molar ratio, by appropriate amount of deionized water stirring and dissolving to clarification, mixed solution is proceeded in the autoclave of inner liner polytetrafluoroethylene, be placed in the baking oven of 200 DEG C, the control reaction time is 12h, question response still naturally cools to room temperature, filter, obtain black precipitate, with deionized water and ethanol repeatedly clean to pH be 7, be positioned over dry 48h in the baking oven of 110 DEG C, obtain black manganese dioxide powder has the radial hollow nano-micro structure formed by nanometer rods self assembly;
In molar ratio Li: Ni: Co: Mn=1.2: 0.136: 0.36: 0.528 take lithium acetate and lithium carbonate mol ratio be 1: 1 mixture, nickel acetate and nickel oxalate mol ratio be 1: 1 mixture, cobalt acetate and cobalt oxalate mol ratio are 1: 1 mixture, manganese dioxide, and in deionized water and alcohol mixed solution Homogeneous phase mixing; Rise to 500 DEG C with 2 DEG C/min heating rate from room temperature, pre-burning 5h, then rise to 800 DEG C with identical heating rate, calcining 10h, obtain the lithium-rich manganese-based anode material with nano-micro structure, chemical formula is 0.5Li
2mnO
30.5LiNi
1/3ni
1/3mn
1/3o
2.
The lithium-rich manganese-based anode material of prepared by the present embodiment have nano-micro structure has homogeneous nano-micro structure, and concrete manifestation is the diameter 15 μm of radial hollow-core constructions formed by the nanometer rods self assembly of diameter 500nm.There is superlattice characteristic peak in the XRD curve of prepared by the present embodiment the have lithium-rich manganese-based anode material of nano-micro structure, illustrates that synthetic material is lithium-rich manganese base material.By the lithium-rich manganese-based anode material assembly simulation lithium ion battery with nano-micro structure obtained, in 2 ~ 4.8V interval, carry out electrochemical property test, carry out with 0.05C activation, first discharge specific capacity can reach 258.2mAh/g; High rate performance test is carried out to the lithium-rich manganese-based anode material assembly simulation lithium ion battery with nano-micro structure prepared by the present embodiment, 0.2,0.5,1,2,5, under 10C specific discharge capacity be about 251 respectively, 229,194,173,141,106mAh/g; Carry out 50 circulations under 5C after, specific discharge capacity can reach 129.4mAh/g, and capability retention is 91.8%.
Claims (9)
1. the preparation method of the high-rate lithium-rich manganese-based anode material of nano-micro structure, the chemical formula of described positive electrode is aLi
2mnO
3(1-a) LiMO
2, wherein 0.3≤a<1, M=Ni
xco
ymn
1-x-y, 0≤x≤0.5,0≤y≤0.5, is characterized in that described method step is as follows:
One, 1:1 ~ 1.5:3 ~ 5 take manganese salt, surfactant and sodium chlorate in molar ratio, by appropriate amount of deionized water stirring and dissolving to clarification, mixed solution is proceeded in the autoclave of inner liner polytetrafluoroethylene, be placed in the baking oven of 150 ~ 200 DEG C, the control reaction time is 10 ~ 16h, question response still naturally cools to room temperature, filter, obtain black precipitate, with deionized water and ethanol repeatedly clean to pH be 6 ~ 8, be positioned over dry 24 ~ 48h in the baking oven of 80 ~ 120 DEG C, obtain black powder manganese dioxide A;
Two, lithium salts, nickel salt, cobalt salt and step one are obtained manganese dioxide A Homogeneous phase mixing, obtain precursor B;
Three, precursor B is put into Muffle furnace air atmosphere, 300 ~ 500 DEG C of pre-burning 3 ~ 8h are risen to from room temperature with 1 ~ 5 DEG C/min heating rate, be warming up to 600 ~ 900 DEG C of calcining 6 ~ 15h with identical heating rate again, obtain the high-rate lithium-rich manganese-based anode material with described nano-micro structure.
2. the preparation method of the high-rate lithium-rich manganese-based anode material of nano-micro structure according to claim 1, is characterized in that described manganese salt is one or more the mixture in manganese sulfate, manganese acetate, manganese oxalate or manganese nitrate.
3. the preparation method of the high-rate lithium-rich manganese-based anode material of nano-micro structure according to claim 1, is characterized in that described surfactant is the one in polyvinylpyrrolidone, DTAB, TTAB, softex kw.
4. the preparation method of the high-rate lithium-rich manganese-based anode material of nano-micro structure according to claim 1, is characterized in that described lithium salts is one or more the mixture in lithium hydroxide, lithium acetate, lithium nitrate, lithium ethoxide, lithium formate, lithium carbonate.
5. the preparation method of the high-rate lithium-rich manganese-based anode material of nano-micro structure according to claim 1, is characterized in that described nickel salt is one or more the mixture in nickelous sulfate, nickel acetate, nickel oxalate or nickel nitrate.
6. the preparation method of the high-rate lithium-rich manganese-based anode material of nano-micro structure according to claim 1, is characterized in that described cobalt salt is one or more the mixture in cobaltous sulfate, cobalt acetate, cobalt oxalate or cobalt nitrate.
7. the preparation method of the high-rate lithium-rich manganese-based anode material of nano-micro structure according to claim 1, it is characterized in that described hybrid mode is liquid phase mixing or solid phase mixing, calcination atmosphere is air.
8. the preparation method of the high-rate lithium-rich manganese-based anode material of nano-micro structure according to claim 1, it is characterized in that described manganese dioxide has the diameter formed by the nanometer rods self assembly of diameter 200 ~ 400nm is 10 ~ 20 μm of radial hollow nano-micro structures.
9. the preparation method of the high-rate lithium-rich manganese-based anode material of nano-micro structure according to claim 1, it is characterized in that described lithium-rich manganese-based anode material has the diameter formed by the nanometer rods self assembly of diameter 200 ~ 400nm is 10 ~ 20 μm of radial hollow nano-micro structures.
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| CN105692703B (en) * | 2014-11-24 | 2017-09-08 | 苏州世名科技股份有限公司 | Lithium-rich manganese-based anode material and preparation method thereof and lithium ion battery |
| CN104900866B (en) * | 2015-04-29 | 2017-07-21 | 哈尔滨工业大学 | A kind of lithium-rich anode material of micro-nano hierarchical structure and preparation method thereof |
| CN105047898B (en) * | 2015-06-05 | 2017-03-01 | 吉林大学 | A kind of twin spherical lithium ion secondary battery lithium-rich anode material and preparation method thereof |
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