CN102916176B - Microsphere laminated lithium-enriched manganese-based solid solution anode material and preparation method thereof - Google Patents

Microsphere laminated lithium-enriched manganese-based solid solution anode material and preparation method thereof Download PDF

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CN102916176B
CN102916176B CN201210435110.1A CN201210435110A CN102916176B CN 102916176 B CN102916176 B CN 102916176B CN 201210435110 A CN201210435110 A CN 201210435110A CN 102916176 B CN102916176 B CN 102916176B
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solution
presoma
preparation
manganese
source compound
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CN102916176A (en
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侯红军
李世江
罗成果
罗传军
杨华春
李云峰
籍兵
靳庆国
许飞
薛旭金
丁运玲
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Multi-fluorine New Energy Technology Co., Ltd.
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Duofuduo (jiaozuo) Amperex Technology Ltd
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    • Y02E60/10Energy storage using batteries

Abstract

The invention discloses a microsphere laminated lithium-enriched manganese-based solid solution anode material, wherein the molecular formula is xLi2Mn1-yNyO3*(1-x)LiMn1-zMzO2; in the formula, M is one or more of Ni and Co; N is one or more of Fe, Cr, Al and Mg; x is more than 0 and less than or equal to 0.3; y is more than 0 and less than or equal to 0.1; and z is more than 0 and less than or equal to 0.7. The invention discloses a preparation method of the material at the same time. The preparation method comprises the following steps of: (1), after co-precipitating a manganese source compound and an M source compound, and sintering the manganese source compound and the M source compound with a lithium source compound in a mixed manner to obtain a precursor 1); (2), sintering the manganese source compound, the lithium source compound and an N element oxide in a mixed manner to obtain a precursor 2); and (3), mixing, acidly washing, spraying and drying the precursor 1) and the precursor 2), and sintering to obtain the lithium-enriched manganese-based solid solution anode material. The microsphere laminated lithium-enriched manganese-based solid solution anode material disclosed by the invention has the advantages of high energy density, good cycle performance, low cost, safety, excellent performance and the like and is applied to the power field with high energy and long service life.

Description

A kind of microballoon stratiform rich lithium manganese base solid solution positive electrode and preparation method thereof
Technical field
The present invention relates to a kind of microballoon stratiform rich lithium manganese base solid solution positive electrode, relate to the preparation method of this material simultaneously, belong to positive electrode field.
Background technology
Along with energy problem to highlight with environmental pollution day by day serious, energy density is high, fail safe is high, volume is little, the lithium battery that has extended cycle life is widely used in the field such as portable type electronic product, electric automobile.
Positive electrode is one of major reason of restriction lithium battery development, and the specific capacity of graphite negative electrodes material is more than 300mAh/g.And the LiCoO of traditional use 2specific discharge capacity only have 160mAh/g, because Co is rare element therefore cost is high, and the poisonous meeting of Co produces certain pollution to environment.LiFePO 4the low and poorly conductive of energy density etc., and when producing, controlled condition is more harsh, and the consistency of material is difficult to control.Stratiform rich lithium manganese base solid solution xLi 2mnO 3(1-x) LiMO 2the reversible specific capacity that discharges under 2.5V ~ 4.6V can reach more than 280mAh/g.This material is mainly based on manganese element, and manganese is cheap, and energy density is higher, more friendly to environment, is one of direction of lithium ion anode material development.
Summary of the invention
The object of this invention is to provide a kind of microballoon stratiform rich lithium manganese base solid solution positive electrode.
In order to realize above object, the technical solution adopted in the present invention is to provide a kind of microballoon stratiform rich lithium manganese base solid solution positive electrode, and the molecular formula of this material is xLi 2mn 1-yn yo 3(1-x) LiMn 1-zm zo 2, in formula, M is one or both in Ni, Co; N is one or more in Fe, Cr, Al, Mg, 0 < x≤0.3,0 < y≤0.1,0 < z≤0.7.
The present invention also aims to the preparation method that a kind of microballoon stratiform rich lithium manganese base solid solution positive electrode is provided.
The technical solution adopted in the present invention is also the preparation method providing a kind of microballoon stratiform rich lithium manganese base solid solution positive electrode, and step is as follows:
1) presoma preparation 1.:
A) preparation of solution:
Solution A: manganese source compound, M source compound are weighed according to manganese, M element mol ratio 1-z:z, add in deionized water and make total concentration 1.0 ~ 4.0mol/L metal salt solution, wherein M is one or both in Ni, Co, 0 < z≤0.7;
Solution B: compound concentration is that the aqueous slkali of 1mol/L ~ 6mol/L is as precipitation reagent;
Solution C: compound concentration is that the ammoniacal liquor of 0.1 ~ 2.0mol/L is as complexing agent;
B) co-precipitation:
Add deionized water in a kettle., bath temperature is 40 ~ 60 DEG C, passes into after inert gas makes reaction environment anaerobic, adds in reactor by solution B and solution C according to volume ratio 1:m, adjust ph 8 ~ 12, rotating speed 100 ~ 200rpm, then pumps into solution A, solution B and solution C in reactor simultaneously, and controlling manganese and the total ion of M metal and mol ratio hydroxy is 1:2, insulation also Keep agitation 2 ~ 8h at 40 ~ 60 DEG C, control solution ph 10 ~ 12, be precipitated, wherein 1≤m≤1.5;
C) presoma process:
Mn (OH) will be precipitated 2with M (OH) 2filter, wash, 90 ~ 110 DEG C of oven dry, add Li source compound according to the ratio of the mol ratio 1-z:z:1 of Mn element, M element, Li element, and ball milling mixes; By 450 ~ 550 DEG C, mixture calcining, 3 ~ 6h, be warming up to 850 ~ 950 DEG C of calcining 5 ~ 20h, 1. cooling obtains precursor naturally;
2) presoma preparation 2.:
A) by Li source compound, manganese source compound, N element oxide according to the ratio mixing and ball milling of the mol ratio 2:1-y:y of Li element, Mn element, N element, wherein, N is one or more in Fe, Cr, Al, Mg, 0 < y≤0.1;
B) presoma process:
Powder step a) obtained mixes, and sinters 5 ~ 72h, obtain presoma 2. under the high temperature of 500 ~ 1000 DEG C;
3) 2. 1. presoma is mixed according to mol ratio 1-x:x with presoma, process with the Acidwash solution that concentration is 0.1 ~ 0.3mol/L, wherein, 0 < x≤0.3;
4) the mixing presoma deionized water of step 3) pickling processes is washed till neutrality, spraying dry after stirring, obtains microspheroidal mixing presoma;
5) by mixing presoma 450 ~ 550 DEG C sintering 3h ~ 10h obtained for step 4), cross 300 mesh sieves after cooling, obtain microballoon stratiform rich lithium manganese base solid solution positive electrode xLi 2mn 1-yn yo 3(1-x) LiMn 1-zm zo 2.
Described manganese source compound is at least one in manganese sulfate, manganese nitrate, manganese acetate, manganese carbonate or manganese dioxide.
Described M source compound is at least one in nickelous sulfate, nickel nitrate, nickel acetate, cobaltous sulfate, cobalt nitrate or cobalt acetate.
Described aqueous slkali is at least one in lithium hydroxide, NaOH or potassium hydroxide.
Described Li source compound is at least one in lithium carbonate, lithium hydroxide or lithium nitrate.
Described N element oxide is at least one in iron oxide, chromium oxide, aluminium oxide or magnesium oxide.
Described Acidwash solution is at least one in nitric acid, sulfuric acid or hydrochloric acid.
Microballoon stratiform rich lithium manganese base solid solution positive electrode prepared by the present invention is a kind of by LiMn 1-zm zo 2and Li 2mn 1-yn yo 3the layed solid-solution that (M is one or both in Ni, Co, and N is one or more in Fe, Cr, Al, Mg, 0 < y≤0.1 in formula, 0 < z≤0.7) is formed, by metallic element N to Li 2mnO 3doping, stablize Li 2mnO 3structure, improve the lattice structure of layered lithium manganate, be conducive to the acid-wash activation to structure, simultaneously can and LiMn 1-zm zo 2form good solid solution.
The present invention adopts spray drying process to prepare micro-spherical particle preparing lithium-rich manganese-based anode material, and have good appearance structure, specific area is less, reduces the dissolving that the contact of electrolyte makes manganese, is conducive to drawing abillity simultaneously.
The advantages such as microballoon stratiform rich lithium manganese base solid solution positive electrode of the present invention, has that energy density is high, good cycle, and with low cost, and security performance is excellent, are applicable to the long-life dynamic field of high-energy.
Accompanying drawing explanation
Fig. 1 is the XRD figure of the rich lithium manganese base solid solution positive electrode of embodiment 1;
Fig. 2 is the SEM figure of the rich lithium manganese base solid solution positive electrode of embodiment 1;
Fig. 3 is the button electricity first charge-discharge figure adopting embodiment 2 rich lithium manganese base solid solution positive electrode to prepare;
Fig. 4 is the button electricity normal temperature cyclic curve adopting embodiment 3 rich lithium manganese base solid solution positive electrode to prepare;
Fig. 5 is the button electricity high temperature circulation curve adopting comparative example rich lithium manganese base solid solution positive electrode to prepare.
Embodiment
Embodiment 1
The molecular formula of the rich lithium manganese base solid solution positive electrode of the present embodiment is 0.3Li 2mn 0.9cr 0.1o 30.7LiMn 0.34ni 0.33co 0.33o 2.
The preparation method of the rich lithium manganese base solid solution positive electrode of the present embodiment, step is as follows:
1) presoma preparation 1.:
A) preparation of solution:
Solution A: by Mn (NO 3) 2, Ni (NO 3) 2, Co (NO 3) 2weigh according to Mn:Ni:Co mol ratio 0.34:0.33:0.33, add in deionized water and make total concentration 1.0mol/L metal salt solution;
Solution B: compound concentration is that 1.0mol/L LiOH solution is as precipitation reagent;
Solution C: compound concentration is that the ammoniacal liquor of 1.0mol/L is as complexing agent;
B) co-precipitation:
Add deionized water 100mL in a kettle., bath temperature is 40 DEG C, pass into after nitrogen makes reaction environment anaerobic, solution B and solution C are added in reactor according to volume ratio 1:1, adjust ph 8, rotating speed 200rpm, then by solution A, solution B and solution C according to pumping in reactor simultaneously, controlling the total ion of nickel Co-Mn metal and mol ratio hydroxy is 1:2, insulation also Keep agitation 8h at 40 DEG C, control solution ph 10, be precipitated;
C) presoma process:
Mn (OH) will be precipitated 2, Ni (OH) 2, Co (OH) 2filter, wash, 100 DEG C of oven dry, add LiOH according to the ratio of the mol ratio 0.34:0.33:0.33:1 of Mn element, Ni element, Co element, Li element, and ball milling mixes; By 500 DEG C, mixture calcining 4.5h, then be warming up to 900 DEG C of calcining 12h, 1. cooling obtains precursor naturally;
2) presoma preparation 2.:
A) batch mixing doping:
By LiOH, MnO 2, Cr 2o 3according to the ratio mixing and ball milling of the mol ratio 2:0.9:0.1 of Li element, Mn element, Cr element;
B) presoma process:
Powder step a) obtained mixes, and sinters 72h, obtain presoma 2. under the high temperature of 500 DEG C;
3) 1. 2. being mixed according to mol ratio 0.7:0.3 with presoma by presoma, is the HNO of 0.1mol/L by concentration 3solution processes;
4) the mixing presoma deionized water of step 3) pickling processes is washed till neutrality, spraying dry after stirring, obtains microspheroidal mixing presoma;
5) by mixing presoma 500 DEG C sintering 7h obtained for step 4), cross 300 mesh sieves after cooling, obtain microballoon stratiform rich lithium manganese base solid solution positive electrode, molecular formula is 0.3Li 2mn 0.9cr 0.1o 30.7LiMn 0.34ni 0.33co 0.33o 2.
The rich lithium manganese base solid solution positive electrode of the present embodiment carries out XRD analysis, as shown in Figure 1.
The rich lithium manganese base solid solution positive electrode of the present embodiment carries out sem analysis, as shown in Figure 2.
Embodiment 2
The molecular formula of the rich lithium manganese base solid solution positive electrode of the present embodiment is 0.2Li 2mn 0.95fe 0.05o 30.8LiMn 0.7ni 0.2co 0.1o 2.
The preparation method of the rich lithium manganese base solid solution positive electrode of the present embodiment, step is as follows:
1) presoma preparation 1.:
A) preparation of solution:
Solution A: by MnSO 4, C 4h 6niO 4, C 4h 6coO 4weigh according to Mn:Ni:Co mol ratio 0.7:0.2:0.1, add in deionized water and make total concentration 3.0mol/L metal salt solution;
Solution B: compound concentration is that 6.0mol/L KOH solution is as precipitation reagent;
Solution C: compound concentration is that the ammoniacal liquor of 0.1mol/L is as complexing agent;
B) co-precipitation:
Add deionized water 100mL in a kettle., bath temperature is 50 DEG C, pass into after argon gas makes reaction environment anaerobic, solution B and solution C are added in reactor according to volume ratio 1:1.25, adjust ph 12, rotating speed 100rpm, then solution A, solution B and solution C are pumped in reactor, the control total ion of nickel Co-Mn metal and mol ratio hydroxy are 1:2 simultaneously, insulation also Keep agitation 2h at 50 DEG C, control solution ph 12, be precipitated;
C) presoma process:
Mn (OH) will be precipitated 2, Ni (OH) 2, Co (OH) 2filter, wash, 110 DEG C of oven dry, add Li according to the ratio of the mol ratio 0.7:0.2:0.1:1 of Mn element, Ni element, Co element, Li element 2cO 3, ball milling mixes; By 550 DEG C, mixture calcining 3h, then be warming up to 850 DEG C of calcining 20h, 1. cooling obtains precursor naturally;
2) presoma preparation 2.:
A) batch mixing doping:
By Li 2cO 3, C 4h 6mnO 4, Fe 2o 3according to the ratio mixing and ball milling of the mol ratio 2:0.95:0.05 of Li element, Mn element, Fe element;
B) presoma process:
Powder step a) obtained mixes, and sinters 40h, obtain presoma 2. under the high temperature of 750 DEG C;
3) 1. 2. being mixed according to mol ratio 0.8:0.2 with presoma by presoma, is the H of 0.3mol/L by concentration 2sO 4solution processes;
4) the mixing presoma deionized water of step 3) pickling processes is washed till neutrality, spraying dry after stirring, obtains microspheroidal mixing presoma;
5) by mixing presoma 550 DEG C sintering 3h obtained for step 4), cross 300 mesh sieves after cooling, obtain microballoon stratiform rich lithium manganese base solid solution positive electrode, molecular formula is 0.2Li 2mn 0.95fe 0.05o 30.8LiMn 0.7ni 0.2co 0.1o 2.
Button electricity charge-discharge property test result prepared by the rich lithium manganese base solid solution positive electrode of the present embodiment, as shown in Figure 3.
Embodiment 3
The molecular formula of the rich lithium manganese base solid solution positive electrode of the present embodiment is 0.1Li 2mn 0.9mg 0.05al 0.05o 30.9LiMn 0.5ni 0.5o 2.
The preparation method of the rich lithium manganese base solid solution positive electrode of the present embodiment, step is as follows:
1) presoma preparation 1.:
A) preparation of solution:
Solution A: by MnCO 3, NiSO 4weigh according to Mn:Ni mol ratio 0.5:0.5, add in deionized water and make total concentration 4.0mol/L metal salt solution;
Solution B: compound concentration is that 4.0mol/L NaOH solution is as precipitation reagent;
Solution C: compound concentration is that the ammoniacal liquor of 2.0mol/L is as complexing agent;
B) co-precipitation:
Add deionized water 100mL in a kettle., bath temperature is 60 DEG C, pass into after nitrogen makes reaction environment anaerobic, solution B and solution C are added in reactor according to volume ratio 1:1.5, adjust ph 10, rotating speed 150rpm, then solution A, solution B and solution C are pumped in reactor, the control nickel total ion of manganese metal and mol ratio hydroxy are 1:2 simultaneously, insulation also Keep agitation 5h at 60 DEG C, control solution ph 11, be precipitated;
C) presoma process:
Mn (OH) will be precipitated 2, Ni (OH) 2filter, wash, 90 DEG C of oven dry, add LiNO according to the ratio of the mol ratio 0.5:0.5:1 of Mn element, Ni element, Li element 3, ball milling mixes; By 450 DEG C, mixture calcining 6h, then be warming up to 950 DEG C of calcining 5h, 1. cooling obtains precursor naturally;
2) presoma preparation 2.:
A) batch mixing doping:
By Li 2cO 3, C 4h 6mnO 4, Al 2o 3, MgO is according to the ratio mixing and ball milling of the mol ratio 2:0.9:0.05:0.05 of Li element, Mn element, Al element and Mg element;
B) presoma process:
Powder step a) obtained mixes, and sinters 5h, obtain presoma 2. under the high temperature of 1000 DEG C;
3) 2. 1. presoma is mixed according to mol ratio 0.9:0.1 with presoma, process with the HCl solution that concentration is 0.2mol/L;
4) the mixing presoma deionized water of step 3) pickling processes is washed till neutrality, spraying dry after stirring, obtains microspheroidal mixing presoma;
5) by mixing presoma 450 DEG C sintering 10h obtained for step 4), cross 300 mesh sieves after cooling, obtain microballoon stratiform rich lithium manganese base solid solution positive electrode, molecular formula is 0.1Li 2mn 0.9mg 0.05al 0.05o 30.9LiMn 0.5ni 0.5o 2.
Button electricity normal temperature cyclic curve prepared by the rich lithium manganese base solid solution positive electrode of the present embodiment, as shown in Figure 4.
Comparative example
The molecular formula of the rich lithium manganese base solid solution positive electrode of this comparative example is 0.3Li 2mnO 30.7LiMn 0.5ni 0.5o 2.
The preparation method of the rich lithium manganese base solid solution positive electrode of this comparative example, step is as follows:
1) presoma preparation 1.:
A) preparation of solution:
Solution A: by Mn (NO 3) 2, Ni (NO 3) 2weigh according to Mn:Ni mol ratio 0.5:0.5, add in deionized water and make total concentration 1.0mol/L metal salt solution;
Solution B: compound concentration is that 2.0mol/L NaOH solution is as precipitation reagent;
Solution C: compound concentration is that the ammoniacal liquor of 0.4mol/L is as complexing agent;
B) co-precipitation:
Add deionized water 100mL in a kettle., bath temperature is 50 DEG C, pass into after nitrogen makes reaction environment anaerobic, solution B and solution C are added in reactor according to volume ratio 1:1, adjust ph 12, rotating speed 200rpm, then solution A, solution B and solution C are pumped in reactor, the control nickel total ion of manganese metal and mol ratio hydroxy are 1:2 simultaneously, insulation also Keep agitation 8h at 50 DEG C, control solution ph 10, be precipitated;
C) presoma process:
Mn (OH) will be precipitated 2, Ni (OH) 2filter, wash, 100 DEG C of oven dry, add Li according to the ratio of the mol ratio 0.5:0.5:1 of Mn element, Ni element, Li element 2cO 3, ball milling mixes; By 500 DEG C, mixture calcining 5h, then be warming up to 900 DEG C of calcining 10h, 1. cooling obtains precursor naturally;
2) presoma preparation 2.:
A) batch mixing doping:
By Li 2cO 3and MnCO 3according to the ratio mixing and ball milling of Li element, Mn elemental mole ratios 2:1;
B) presoma process:
Powder step a) obtained mixes, and sinters 36h, obtain presoma 2. under the high temperature of 500 DEG C;
3) 1. 2. being mixed according to mol ratio 0.7:0.3 with presoma by presoma, is the HNO of 0.1mol/L by concentration 3solution processes;
4) the mixing presoma deionized water of step 3) pickling processes is washed till neutrality, spraying dry after stirring, obtains microspheroidal mixing presoma;
5) by mixing presoma 500 DEG C sintering 10h obtained for step 4), cross 300 mesh sieves after cooling, obtain microballoon stratiform rich lithium manganese base solid solution positive electrode, molecular formula is 0.3Li 2mnO 30.7LiMn 0.5ni 0.5o 2.
Button electricity high temperature circulation curve prepared by the rich lithium manganese base solid solution positive electrode of comparative example, as shown in Figure 5.
Rich lithium manganese base solid solution positive electrode electric property comparative analysis to embodiment 1-3 and comparative example:
The rich lithium manganese base solid solution positive electrode of embodiment 1 ~ 3 and comparative example is made into 2032 type button cell test results, as shown in table 1,2.
The measurement result of the battery that the rich lithium manganese base solid solution positive electrode of table 1 embodiment 1 ~ 3 and comparative example is made
The measurement result of the battery that the rich lithium manganese base solid solution positive electrode of table 2 embodiment 1 ~ 3 and comparative example is made
2032 type button cells prepared by rich lithium manganese base solid solution positive electrode of the present invention, battery core carries out discharge and recharge at 2.5 ~ 4.6V voltage range, and charge and discharge efficiency first reaches more than 95%; 0.2C electric discharge gram volume plays more than 209mAh/g.Battery has excellent cycle performance, and under 2.5 ~ 4.3V, normal temperature, 0.5C charge and discharge 100 capacity that circulate remain on more than 90%; At high temperature 55 DEG C, 0.5C 300 capacity that circulate remain on more than 80%; Under 3C multiplying power, electric discharge is more than 90% of 1C capacity.
The present invention has the following advantages:
1, reversible discharge capacity is higher and gram volume is higher first.
2, under normal temperature environment, cycle performance is better, and doped metal ion makes the structure of material more stable.
3, under normal temperature environment, high rate performance is higher.
4, under hot environment, cycle performance is more superior, effectively prevents the structure of material from high temperature changing.

Claims (8)

1. a microballoon stratiform rich lithium manganese base solid solution positive electrode, is characterized in that, the molecular formula of this material is xLi 2mn 1-yn yo 3(1-x) LiMn 1-zm zo 2, in formula, M is one or both in Ni, Co; N is one or more in Fe, Cr, Al, Mg, 0 < x≤0.3,0 < y≤0.1,0 < z≤0.7;
Preparation method's step of described microballoon stratiform rich lithium manganese base solid solution positive electrode is as follows:
1) presoma preparation 1.:
A) preparation of solution:
Solution A: manganese source compound, M source compound are weighed according to manganese, M element mol ratio 1-z:z, add in deionized water and make total concentration 1.0 ~ 4.0mol/L metal salt solution, wherein M is one or both in Ni, Co, 0 < z≤0.7;
Solution B: compound concentration is that the aqueous slkali of 1mol/L ~ 6mol/L is as precipitation reagent;
Solution C: compound concentration is that the ammoniacal liquor of 0.1 ~ 2.0mol/L is as complexing agent;
B) co-precipitation:
Add deionized water in a kettle., bath temperature is 40 ~ 60 DEG C, pass into after inert gas makes reaction environment anaerobic, solution B and solution C are added in reactor according to volume ratio 1:m, adjust ph 8 ~ 12, rotating speed 100 ~ 200rpm, then solution A, solution B and solution C are pumped in reactor simultaneously, controlling manganese and the total ion of M metal and mol ratio hydroxy is 1:2, insulation also Keep agitation 2 ~ 8h at 40 ~ 60 DEG C, control solution ph 10 ~ 12, be precipitated, wherein 1≤m≤1.5;
C) presoma process:
Mn (OH) will be precipitated 2with M (OH) 2filter, wash, 90 ~ 110 DEG C of oven dry, add Li source compound according to the ratio of the mol ratio 1-z:z:1 of Mn element, M element, Li element, and ball milling mixes; By 450 ~ 550 DEG C, mixture calcining, 3 ~ 6h, be warming up to 850 ~ 950 DEG C of calcining 5 ~ 20h, 1. cooling obtains precursor naturally;
2) presoma preparation 2.:
A) by Li source compound, manganese source compound, N element oxide according to the ratio mixing and ball milling of the mol ratio 2:1-y:y of Li element, Mn element, N element, wherein, N is one or more in Fe, Cr, Al, Mg, 0 < y≤0.1;
B) presoma process:
Powder step a) obtained mixes, and sinters 5 ~ 72h, obtain presoma 2. under the high temperature of 500 ~ 1000 DEG C;
3) 2. 1. presoma is mixed according to mol ratio 1-x:x with presoma, process with the Acidwash solution that concentration is 0.1 ~ 0.3mol/L, wherein, 0 < x≤0.3;
4) by step 3) the mixing presoma deionized water of pickling processes is washed till neutrality, spraying dry after stirring, and obtains microspheroidal mixing presoma;
5) by step 4) obtained mixing presoma 450 ~ 550 DEG C sintering 3h ~ 10h, crosses 300 mesh sieves after cooling, obtains microballoon stratiform rich lithium manganese base solid solution positive electrode xLi 2mn 1-yn yo 3(1-x) LiMn 1-zm zo 2.
2. a preparation method for microballoon stratiform rich lithium manganese base solid solution positive electrode as claimed in claim 1, it is characterized in that, step is as follows:
1) presoma preparation 1.:
A) preparation of solution:
Solution A: manganese source compound, M source compound are weighed according to manganese, M element mol ratio 1-z:z, add in deionized water and make total concentration 1.0 ~ 4.0mol/L metal salt solution, wherein M is one or both in Ni, Co, 0 < z≤0.7;
Solution B: compound concentration is that the aqueous slkali of 1mol/L ~ 6mol/L is as precipitation reagent;
Solution C: compound concentration is that the ammoniacal liquor of 0.1 ~ 2.0mol/L is as complexing agent;
B) co-precipitation:
Add deionized water in a kettle., bath temperature is 40 ~ 60 DEG C, pass into after inert gas makes reaction environment anaerobic, solution B and solution C are added in reactor according to volume ratio 1:m, adjust ph 8 ~ 12, rotating speed 100 ~ 200rpm, then solution A, solution B and solution C are pumped in reactor simultaneously, controlling manganese and the total ion of M metal and mol ratio hydroxy is 1:2, insulation also Keep agitation 2 ~ 8h at 40 ~ 60 DEG C, control solution ph 10 ~ 12, be precipitated, wherein 1≤m≤1.5;
C) presoma process:
Mn (OH) will be precipitated 2with M (OH) 2filter, wash, 90 ~ 110 DEG C of oven dry, add Li source compound according to the ratio of the mol ratio 1-z:z:1 of Mn element, M element, Li element, and ball milling mixes; By 450 ~ 550 DEG C, mixture calcining, 3 ~ 6h, be warming up to 850 ~ 950 DEG C of calcining 5 ~ 20h, 1. cooling obtains precursor naturally;
2) presoma preparation 2.:
A) by Li source compound, manganese source compound, N element oxide according to the ratio mixing and ball milling of the mol ratio 2:1-y:y of Li element, Mn element, N element, wherein, N is one or more in Fe, Cr, Al, Mg, 0 < y≤0.1;
B) presoma process:
Powder step a) obtained mixes, and sinters 5 ~ 72h, obtain presoma 2. under the high temperature of 500 ~ 1000 DEG C;
3) 2. 1. presoma is mixed according to mol ratio 1-x:x with presoma, process with the Acidwash solution that concentration is 0.1 ~ 0.3mol/L, wherein, 0 < x≤0.3;
4) by step 3) the mixing presoma deionized water of pickling processes is washed till neutrality, spraying dry after stirring, and obtains microspheroidal mixing presoma;
5) by step 4) obtained mixing presoma 450 ~ 550 DEG C sintering 3h ~ 10h, crosses 300 mesh sieves after cooling, obtains microballoon stratiform rich lithium manganese base solid solution positive electrode xLi 2mn 1-yn yo 3(1-x) LiMn 1-zm zo 2.
3. the preparation method of a kind of microballoon stratiform rich lithium manganese base solid solution positive electrode according to claim 2, it is characterized in that, described manganese source compound is at least one in manganese sulfate, manganese nitrate, manganese acetate, manganese carbonate or manganese dioxide.
4. the preparation method of a kind of microballoon stratiform rich lithium manganese base solid solution positive electrode according to claim 2, it is characterized in that, described M source compound is at least one in nickelous sulfate, nickel nitrate, nickel acetate, cobaltous sulfate, cobalt nitrate or cobalt acetate.
5. the preparation method of a kind of microballoon stratiform rich lithium manganese base solid solution positive electrode according to claim 2, it is characterized in that, described aqueous slkali is at least one in lithium hydroxide, NaOH or potassium hydroxide.
6. the preparation method of a kind of microballoon stratiform rich lithium manganese base solid solution positive electrode according to claim 2, it is characterized in that, described Li source compound is at least one in lithium carbonate, lithium hydroxide or lithium nitrate.
7. the preparation method of a kind of microballoon stratiform rich lithium manganese base solid solution positive electrode according to claim 2, it is characterized in that, described N element oxide is at least one in iron oxide, chromium oxide, aluminium oxide or magnesium oxide.
8. the preparation method of a kind of microballoon stratiform rich lithium manganese base solid solution positive electrode according to claim 2, it is characterized in that, described Acidwash solution is at least one in nitric acid, sulfuric acid or hydrochloric acid.
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