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 PDFInfo
- Publication number
- 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
- Authority
- CN
- China
- Prior art keywords
- solution
- presoma
- preparation
- manganese
- source compound
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Battery Electrode And Active Subsutance (AREA)
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
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.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210435110.1A CN102916176B (en) | 2012-11-02 | 2012-11-02 | Microsphere laminated lithium-enriched manganese-based solid solution anode material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210435110.1A CN102916176B (en) | 2012-11-02 | 2012-11-02 | Microsphere laminated lithium-enriched manganese-based solid solution anode material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102916176A CN102916176A (en) | 2013-02-06 |
| CN102916176B true CN102916176B (en) | 2015-06-17 |
Family
ID=47614473
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210435110.1A Active CN102916176B (en) | 2012-11-02 | 2012-11-02 | Microsphere laminated lithium-enriched manganese-based solid solution anode material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102916176B (en) |
Families Citing this family (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103232069A (en) * | 2013-03-20 | 2013-08-07 | 江苏凯力克钴业股份有限公司 | Lithium ion battery lithium-rich manganese base positive electrode material preparation method |
| KR101675951B1 (en) * | 2014-03-12 | 2016-11-17 | 서울대학교산학협력단 | Cathode Active Material and Lithium Secondary Battery Comprising the Same |
| CN108091858B (en) * | 2017-12-14 | 2022-09-13 | 桑顿新能源科技(长沙)有限公司 | Li-O-site lithium manganate-doped lithium-rich cathode material and preparation method thereof |
| CN108172823B (en) * | 2018-01-26 | 2021-05-25 | 浙江吉利汽车研究院有限公司 | Lithium-manganese-rich material, lithium ion battery positive electrode plate, lithium ion battery and preparation method thereof |
| CN108448109B (en) * | 2018-03-23 | 2021-07-02 | 中南大学 | Layered lithium-rich manganese-based positive electrode material and preparation method thereof |
| CN108767229B (en) * | 2018-05-30 | 2021-03-23 | 天津巴莫科技股份有限公司 | Step-by-step composite lithium-rich oxide solid solution material and preparation method thereof |
| CN109778301A (en) * | 2019-01-03 | 2019-05-21 | 北京工业大学 | The preparation of one type monocrystalline lithium-rich oxide material and application |
| CN110165181A (en) * | 2019-05-29 | 2019-08-23 | 华东理工大学 | A kind of lithium-rich manganese-based/grapheme composite positive electrode material, preparation method and applications |
| CN112062167B (en) * | 2020-08-28 | 2023-09-22 | 常熟理工学院 | Micron-sized binary doped lithium-rich material and preparation method and application thereof |
| CN113851641A (en) * | 2021-09-17 | 2021-12-28 | 天津市捷威动力工业有限公司 | High-entropy solid solution cathode material and preparation method and application thereof |
| CN114455638B (en) * | 2021-12-28 | 2023-11-10 | 天津巴莫科技有限责任公司 | Solid electrolyte material with high lithium ion diffusivity and preparation method thereof |
| CN114804227B (en) * | 2022-04-24 | 2023-07-07 | 南通金通储能动力新材料有限公司 | Layered structure sodium ion battery positive electrode material precursor and preparation method thereof |
| CN115403075A (en) * | 2022-08-16 | 2022-11-29 | 西南石油大学 | Cobalt-free quaternary lithium-rich manganese-based positive electrode material and preparation method thereof |
| CN115818738A (en) * | 2023-02-16 | 2023-03-21 | 国联汽车动力电池研究院有限责任公司 | Method for modifying lithium-rich manganese-based positive electrode material by using multi-component gas |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101409342A (en) * | 2008-10-31 | 2009-04-15 | 深圳市贝特瑞新能源材料股份有限公司 | Method for preparing composite anode material |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101694876A (en) * | 2009-10-22 | 2010-04-14 | 江西江特锂电池材料有限公司 | Lithium-rich manganese-based anode material and preparation method thereof |
| CN101707252B (en) * | 2009-11-09 | 2012-01-25 | 深圳市振华新材料股份有限公司 | Polycrystal Co-Ni-Mn ternary anode material and preparation method thereof as well as secondary lithium-ion battery |
| CN101764222B (en) * | 2009-12-22 | 2011-11-09 | 深圳市振华新材料股份有限公司 | High-manganese polycrystalline cathode material, preparation method thereof and power lithium-ion battery |
| CN102751483A (en) * | 2012-07-18 | 2012-10-24 | 中国科学院福建物质结构研究所 | Layered rich-lithium-manganese-based solid-solution anode material of lithium ion battery and method for preparing anode material |
-
2012
- 2012-11-02 CN CN201210435110.1A patent/CN102916176B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101409342A (en) * | 2008-10-31 | 2009-04-15 | 深圳市贝特瑞新能源材料股份有限公司 | Method for preparing composite anode material |
Non-Patent Citations (1)
| Title |
|---|
| Fe content effects on electrochemical properties of Fe-substituted Li2MnO3 positive electrode material;Mitsuharu Tabuchia、Yoko Nabeshima、Tomonari Takeuchia;《Journal of Power Sources》;20090831;第195卷(第2010期);第837页左栏第一段，第844页的第4部分结论部分和图4 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102916176A (en) | 2013-02-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102916176B (en) | Microsphere laminated lithium-enriched manganese-based solid solution anode material and preparation method thereof | |
| CN108091843B (en) | Lithium-rich manganese-based composite cathode material with core-shell structure and preparation method thereof | |
| CN104157831B (en) | Lithium-rich manganese-based composite positive pole of the spinel nickel LiMn2O4 of a kind of core shell structure, stratiform and preparation method thereof | |
| CN102074679B (en) | Method for preparing spherical aluminum-doped nickel lithium carbonate for lithium ion battery positive electrode material | |
| CN102751480B (en) | A kind of cladded type lithium-rich manganese base material and preparation method thereof | |
| CN102315429B (en) | The preparation method of aluminum-doped material of cathode of lithium ion battery with solid phase process | |
| CN102983326B (en) | Spherical lithium-nickel-cobalt composite oxide positive electrode material preparation method | |
| CN103762353B (en) | A kind of heterogeneous nucleocapsid structure high-capacity lithium ion battery electricity positive electrode with and preparation method thereof | |
| CN104701530A (en) | Preparation method of in-situ doped and modified nickel cobalt manganese lithium oxide positive material | |
| CN102244236A (en) | Method for preparing lithium-enriched cathodic material of lithium ion battery | |
| CN102683645A (en) | Preparation method of layered lithium-rich manganese base oxide of positive material of lithium ion battery | |
| CN103117380A (en) | Preparation method of manganese Li-NiCoMn ternary material for lithium ion battery | |
| CN101997113A (en) | Multicomponent material with multilayer coating structure for lithium ion battery and preparation method thereof | |
| CN102208607A (en) | Synthesis and surface modification method of lithium excessive laminar oxide anode material | |
| CN102623691B (en) | Method for preparing lithium nickel manganese oxide serving as cathode material of lithium battery | |
| CN109088067B (en) | Preparation method of low-cobalt-doped spinel-layered-structure lithium nickel manganese oxide two-phase composite positive electrode material | |
| CN105514373A (en) | Positive electrode material of high-capacity lithium ion battery and preparation method of positive electrode material | |
| CN103647070B (en) | A kind of rare earth samarium is modified the preparation method of tertiary cathode material | |
| CN103094554B (en) | Modified lithium manganate anode material and preparation method thereof | |
| CN103413926B (en) | Preparation method of lithium nickel cobalt manganese oxide precursor | |
| CN102838169B (en) | Preparation method of iron-containing lithium-rich manganese-based positive electrode material | |
| CN103606667A (en) | Preparation method for manganese solid solution anode material of lithium ion battery material | |
| CN102832387B (en) | Layer-structured ternary material with rich lithium and high manganese as well as preparation method and application thereof | |
| CN102730761A (en) | Oxalate coprecipitation preparation method for high-capacity lithium-rich cathode material | |
| CN103178252B (en) | A kind of anode material for lithium-ion batteries and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| ASS | Succession or assignment of patent right |
Owner name: JIAOZUO BANLV NANO MATERIAL ENGINEERING CO., LTD. Free format text: FORMER OWNER: DUO-FLUORIDE CHEMICALS CO., LTD. Effective date: 20131108 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20131108 Address after: 454191 Henan Province, Jiaozuo City Station area one middle Jiao Applicant after: JIAOZUO BANLV NANO MATERIAL ENGINEERING COMPANY LIMITED Address before: The station area 454191 Henan province Jiaozuo City West Feng Feng Industrial Zone Applicant before: Duo-fluoride Chemicals Co., Ltd. |
|
| ASS | Succession or assignment of patent right |
Owner name: DO FLUORIDE (JIAOZUO) NEW ENERGY TECHNOLOGY CO., L Free format text: FORMER OWNER: JIAOZUO BANLV NANO MATERIAL ENGINEERING CO., LTD. Effective date: 20150504 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| C53 | Correction of patent for invention or patent application | ||
| CB03 | Change of inventor or designer information |
Inventor after: Hou Hongjun Inventor after: Xue Xujin Inventor after: Ding Yunling Inventor after: Li Shijiang Inventor after: Luo Chengguo Inventor after: Luo Chuanjun Inventor after: Yang Huachun Inventor after: Li Yunfeng Inventor after: Ji Bing Inventor after: Jin Qingguo Inventor after: Xu Fei Inventor before: Hou Hongjun Inventor before: Li Shijiang Inventor before: Luo Chengguo Inventor before: Luo Chuanjun Inventor before: Yang Huachun Inventor before: Li Yunfeng Inventor before: Xue Xujin Inventor before: Ding Yunling Inventor before: Zhao Yongfeng |
|
| COR | Change of bibliographic data |
Free format text: CORRECT: INVENTOR; FROM: HOU HONGJUN LI SHIJIANG LUO CHENGGUO LUO CHUANJUN YANG HUACHUN LI YUNFENG XUE XUJIN DING YUNLING ZHAO YONGFENG TO: HOU HONGJUN LI SHIJIANG LUO CHENGGUO LUO CHUANJUN YANG HUACHUN LI YUNFENG JI BING JIN GUOQING XU FEI XUE XUJIN DING YUNLING |
|
| TA01 | Transfer of patent application right |
Effective date of registration: 20150504 Address after: Jiaozuo City, the 454191 industrial agglomeration area in Henan province of North Park Road West Park District Building Standard Applicant after: Duofuduo (Jiaozuo) Amperex Technology Limited Address before: 454191 Henan Province, Jiaozuo City Station area one middle Jiao Applicant before: JIAOZUO BANLV NANO MATERIAL ENGINEERING COMPANY LIMITED |
|
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CP01 | Change in the name or title of a patent holder |
Address after: 454191 Industrial Cluster Area, Jiaozuo City, Henan Province, Standardized Workshop Area on the North Side of Xinyuan Road, West Park Patentee after: Multi-fluorine New Energy Technology Co., Ltd. Address before: 454191 Industrial Cluster Area, Jiaozuo City, Henan Province, Standardized Workshop Area on the North Side of Xinyuan Road, West Park Patentee before: Duofuduo (Jiaozuo) Amperex Technology Limited |
|
| CP01 | Change in the name or title of a patent holder |