CN102916176A - 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
- CN102916176A CN102916176A CN2012104351101A CN201210435110A CN102916176A CN 102916176 A CN102916176 A CN 102916176A CN 2012104351101 A CN2012104351101 A CN 2012104351101A CN 201210435110 A CN201210435110 A CN 201210435110A CN 102916176 A CN102916176 A CN 102916176A
- Authority
- CN
- China
- Prior art keywords
- manganese
- lithium
- solution
- preparation
- presoma
- 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.)
- Granted
Links
Images
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 the lithium-rich manganese-based solid solution cathode material of a kind of microballoon stratiform, relate to simultaneously this material preparation method, belong to the positive electrode field.
Background technology
Along with day by day serious with environmental pollution of highlighting of energy problem, the lithium battery that energy density is high, safe, volume is little, have extended cycle life is widely used in the fields 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 has surpassed 300mAh/g.And the LiCoO of traditional use
2Specific discharge capacity only have 160mAh/g cost is high because Co is rare element, and the poisonous meeting of Co produces certain pollution to environment.LiFePO
4The low and poorly conductive of energy density etc., and controlled condition is more harsh when producing, the consistency of material is difficult to control.The lithium-rich manganese-based solid solution xLi of stratiform
2MnO
3(1-x) LiMO
2The discharge reversible specific capacity can reach more than the 280mAh/g under 2.5V～4.6V.This material mainly is take manganese element as main, and manganese is cheap, and energy density is higher, and is more friendly to environment, is one of direction of lithium ion anode material development.
Summary of the invention
The purpose of this invention is to provide the lithium-rich manganese-based solid solution cathode material of a kind of microballoon stratiform.
In order to realize above purpose, the technical solution adopted in the present invention provides the lithium-rich manganese-based solid solution cathode material of a kind of microballoon stratiform, and the molecular formula of this material is xLi
2Mn
1-yN
yO
3(1-x) LiMn
1-zM
zO
2, M is one or both among Ni, the Co in the formula; N is one or more among Fe, Cr, Al, the Mg, 0＜x≤0.3,0＜y≤0.1,0＜z≤0.7.
The present invention also aims to provide the preparation method of the lithium-rich manganese-based solid solution cathode material of a kind of microballoon stratiform.
The technical solution adopted in the present invention also is to provide the preparation method of the lithium-rich manganese-based solid solution cathode material of a kind of microballoon stratiform, and step is as follows:
1) presoma preparation 1.:
A) preparation of solution:
Solution A: manganese source compound, M source compound according to manganese, M element mol ratio 1-z:z weighing, are added in the deionized water and make total concentration 1.0～4.0mol/L metal salt solution, and wherein M is one or both among Ni, the 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:
In reactor, add deionized water, bath temperature is 40～60 ℃, after passing into inert gas and making the reaction environment anaerobic, solution B and solution C is added in the reactor according to volume ratio 1:m, regulate pH value 8～12, then rotating speed 100 ~ 200rpm pumps into solution A, solution B and solution C in the reactor simultaneously, and control manganese and the total ion of M metal and mol ratio hydroxy are 1:2, at 40～60 ℃ of lower insulations and the lasting 2 ~ 8h that stirs, the control pH is precipitated, wherein 1≤m≤1.5 10～12;
C) presoma is processed:
To precipitate Mn (OH)
2And M (OH)
2Filter, washing, 90～110 ℃ 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, ball milling mixes; With 450～550 ℃ of calcinings of mixture, 3～6h, be warming up to 850～950 ℃ of calcining 5～20h, 1. cooling obtains precursor naturally;
2) presoma preparation 2.:
A) with Li source compound, manganese source compound, the N element oxide ratio mixing and ball milling according to the mol ratio 2:1-y:y of Li element, Mn element, N element, wherein, N is one or more among Fe, Cr, Al, the Mg, 0＜y≤0.1;
B) presoma is processed:
The powder that step a) is obtained mixes, and 2. sintering 5～72h under 500～1000 ℃ high temperature gets presoma;
3) 2. 1. presoma being mixed according to mol ratio 1-x:x with presoma, is that the Acidwash solution of 0.1～0.3mol/L is processed with concentration, wherein, and 0＜x≤0.3;
4) the mixing presoma with the step 3) pickling processes is washed till neutrality with deionized water, and the rear spray drying that stirs obtains microspheroidal and mixes presoma;
5) 450～550 ℃ of sintering 3h～10h of the mixing presoma that step 4) is made cross 300 mesh sieves after the cooling, obtain the lithium-rich manganese-based solid solution cathode material xLi of microballoon stratiform
2Mn
1-yN
yO
3(1-x) LiMn
1-zM
zO
2
Described manganese source compound is at least a in manganese sulfate, manganese nitrate, manganese acetate, manganese carbonate or the manganese dioxide.
Described M source compound is at least a in nickelous sulfate, nickel nitrate, nickel acetate, cobaltous sulfate, cobalt nitrate or the cobalt acetate.
Described aqueous slkali is at least a in lithium hydroxide, NaOH or the potassium hydroxide.
Described Li source compound is at least a in lithium carbonate, lithium hydroxide or the lithium nitrate.
Described N element oxide is at least a in iron oxide, chromium oxide, aluminium oxide or the magnesium oxide.
Described Acidwash solution is at least a in nitric acid, sulfuric acid or the hydrochloric acid.
The lithium-rich manganese-based solid solution cathode material of microballoon stratiform of the present invention's preparation 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 among Ni, the Co, and N is one or more among Fe, Cr, Al, the Mg, 0＜y in the formula≤0.1,0＜z≤0.7) forms, 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 solutionizing compound.
The present invention adopts spray drying process to prepare micro-spherical particle at the preparation lithium-rich manganese-based anode material, has good appearance structure, and specific area is less, and the contact that reduces electrolyte makes the dissolving of manganese, is conducive to simultaneously drawing abillity.
The lithium-rich manganese-based solid solution cathode material of microballoon stratiform of the present invention has that energy density is high, good cycle, and with low cost, and the advantages such as security performance excellence are applicable to the long-life power of high-energy field.
Description of drawings
Fig. 1 is the XRD figure of the lithium-rich manganese-based solid solution cathode material of embodiment 1;
Fig. 2 is the SEM figure of the lithium-rich manganese-based solid solution cathode material of embodiment 1;
Fig. 3 is for adopting the button electricity first charge-discharge figure of embodiment 2 lithium-rich manganese-based solid solution cathode material preparations;
Fig. 4 is for adopting the button electricity normal temperature cyclic curve of embodiment 3 lithium-rich manganese-based solid solution cathode material preparations;
Fig. 5 is for adopting the button electricity high temperature circulation curve of the lithium-rich manganese-based solid solution cathode material preparation of Comparative Examples.
Embodiment
The molecular formula of the lithium-rich manganese-based solid solution cathode material 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 lithium-rich manganese-based solid solution cathode material of the present embodiment, step is as follows:
1) presoma preparation 1.:
A) preparation of solution:
Solution A: with Mn (NO
3)
2, Ni (NO
3)
2, Co (NO
3)
2According to Mn:Ni:Co mol ratio 0.34:0.33:0.33 weighing, add in the 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:
In reactor, add deionized water 100mL, bath temperature is 40 ℃, after passing into nitrogen and making the reaction environment anaerobic, solution B and solution C are added in the reactor according to volume ratio 1:1, regulate pH value 8, rotating speed 200rpm, then with solution A, solution B and solution C according to pumping into simultaneously in the reactor, the control total ion of nickel Co-Mn metal is 1:2 with mol ratio hydroxy, 40 ℃ of lower insulations and continue stirring 8h, control pH 10 is precipitated;
C) presoma is processed:
To precipitate Mn (OH)
2, Ni (OH)
2, Co (OH)
2Filter, washing, 100 ℃ 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, ball milling mixes; With 500 ℃ of calcinings of mixture 4.5h, be warming up to again 900 ℃ of calcining 12h, 1. cooling obtains precursor naturally;
2) presoma preparation 2.:
A) batch mixing mixes:
With LiOH, MnO
2, Cr
2O
3Ratio mixing and ball milling according to the mol ratio 2:0.9:0.1 of Li element, Mn element, Cr element;
B) presoma is processed:
The powder that step a) is obtained mixes, and 2. sintering 72h under 500 ℃ high temperature gets presoma;
3) 2. 1. presoma being mixed according to mol ratio 0.7:0.3 with presoma, is the HNO of 0.1mol/L with concentration
3Solution is processed;
4) the mixing presoma with the step 3) pickling processes is washed till neutrality with deionized water, and the rear spray drying that stirs obtains microspheroidal and mixes presoma;
5) 500 ℃ of sintering 7h of the mixing presoma that step 4) is made cross 300 mesh sieves after the cooling, obtain the lithium-rich manganese-based solid solution cathode material of microballoon stratiform, and molecular formula is 0.3Li
2Mn
0.9Cr
0.1O
30.7LiMn
0.34Ni
0.33Co
0.33O
2
The lithium-rich manganese-based solid solution cathode material of the present embodiment carries out XRD analysis, as shown in Figure 1.
The lithium-rich manganese-based solid solution cathode material of the present embodiment carries out sem analysis, as shown in Figure 2.
The molecular formula of the lithium-rich manganese-based solid solution cathode material 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 lithium-rich manganese-based solid solution cathode material of the present embodiment, step is as follows:
1) presoma preparation 1.:
A) preparation of solution:
Solution A: with MnSO
4, C
4H
6NiO
4, C
4H
6CoO
4According to Mn:Ni:Co mol ratio 0.7:0.2:0.1 weighing, add in the 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:
In reactor, add deionized water 100mL, bath temperature is 50 ℃, after passing into argon gas and making the reaction environment anaerobic, solution B and solution C are added in the reactor according to volume ratio 1:1.25, regulate pH value 12, rotating speed 100rpm, then solution A, solution B and solution C are pumped in the reactor simultaneously, the control total ion of nickel Co-Mn metal and mol ratio hydroxy are 1:2, at 50 ℃ of lower insulations and the lasting 2h that stirs, the control pH is precipitated 12;
C) presoma is processed:
To precipitate Mn (OH)
2, Ni (OH)
2, Co (OH)
2Filter, washing, 110 ℃ 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; With 550 ℃ of calcinings of mixture 3h, be warming up to again 850 ℃ of calcining 20h, 1. cooling obtains precursor naturally;
2) presoma preparation 2.:
A) batch mixing mixes:
With Li
2CO
3, C
4H
6MnO
4, Fe
2O
3Ratio mixing and ball milling according to the mol ratio 2:0.95:0.05 of Li element, Mn element, Fe element;
B) presoma is processed:
The powder that step a) is obtained mixes, and 2. sintering 40h under 750 ℃ high temperature gets presoma;
3) 2. 1. presoma being mixed according to mol ratio 0.8:0.2 with presoma, is the H of 0.3mol/L with concentration
2SO
4Solution is processed;
4) the mixing presoma with the step 3) pickling processes is washed till neutrality with deionized water, and the rear spray drying that stirs obtains microspheroidal and mixes presoma;
5) 550 ℃ of sintering 3h of the mixing presoma that step 4) is made cross 300 mesh sieves after the cooling, obtain the lithium-rich manganese-based solid solution cathode material of microballoon stratiform, and molecular formula is 0.2Li
2Mn
0.95Fe
0.05O
30.8LiMn
0.7Ni
0.2Co
0.1O
2
The button electricity charge-discharge property test result of the lithium-rich manganese-based solid solution cathode material preparation of the present embodiment, as shown in Figure 3.
Embodiment 3
The molecular formula of the lithium-rich manganese-based solid solution cathode material 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 lithium-rich manganese-based solid solution cathode material of the present embodiment, step is as follows:
1) presoma preparation 1.:
A) preparation of solution:
Solution A: with MnCO
3, NiSO
4According to Mn:Ni mol ratio 0.5:0.5 weighing, add in the 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:
In reactor, add deionized water 100mL, bath temperature is 60 ℃, after passing into nitrogen and making the reaction environment anaerobic, solution B and solution C are added in the reactor according to volume ratio 1:1.5, regulate pH value 10, rotating speed 150rpm, then solution A, solution B and solution C are pumped in the reactor simultaneously, the control nickel total ion of manganese metal and mol ratio hydroxy are 1:2, at 60 ℃ of lower insulations and the lasting 5h that stirs, the control pH is precipitated 11;
C) presoma is processed:
To precipitate Mn (OH)
2, Ni (OH)
2Filter, washing, 90 ℃ 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; With 450 ℃ of calcinings of mixture 6h, be warming up to again 950 ℃ of calcining 5h, 1. cooling obtains precursor naturally;
2) presoma preparation 2.:
A) batch mixing mixes:
With 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 is processed:
The powder that step a) is obtained mixes, and 2. sintering 5h under 1000 ℃ high temperature gets presoma;
3) 2. 1. presoma being mixed according to mol ratio 0.9:0.1 with presoma, is that the HCl solution of 0.2mol/L is processed with concentration;
4) the mixing presoma with the step 3) pickling processes is washed till neutrality with deionized water, and the rear spray drying that stirs obtains microspheroidal and mixes presoma;
5) 450 ℃ of sintering 10h of the mixing presoma that step 4) is made cross 300 mesh sieves after the cooling, obtain the lithium-rich manganese-based solid solution cathode material of microballoon stratiform, and molecular formula is 0.1Li
2Mn
0.9Mg
0.05Al
0.05O
30.9LiMn
0.5Ni
0.5O
2
The button electricity normal temperature cyclic curve of the lithium-rich manganese-based solid solution cathode material preparation of the present embodiment, as shown in Figure 4.
Comparative Examples
The molecular formula of the lithium-rich manganese-based solid solution cathode material of this Comparative Examples is 0.3Li
2MnO
30.7LiMn
0.5Ni
0.5O
2
The preparation method of the lithium-rich manganese-based solid solution cathode material of this Comparative Examples, step is as follows:
1) presoma preparation 1.:
A) preparation of solution:
Solution A: with Mn (NO
3)
2, Ni (NO
3)
2According to Mn:Ni mol ratio 0.5:0.5 weighing, add in the 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:
In reactor, add deionized water 100mL, bath temperature is 50 ℃, after passing into nitrogen and making the reaction environment anaerobic, solution B and solution C are added in the reactor according to volume ratio 1:1, regulate pH value 12, rotating speed 200rpm, then solution A, solution B and solution C are pumped in the reactor simultaneously, the control nickel total ion of manganese metal and mol ratio hydroxy are 1:2, at 50 ℃ of lower insulations and the lasting 8h that stirs, the control pH is precipitated 10;
C) presoma is processed:
To precipitate Mn (OH)
2, Ni (OH)
2Filter, washing, 100 ℃ 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; With 500 ℃ of calcinings of mixture 5h, be warming up to again 900 ℃ of calcining 10h, 1. cooling obtains precursor naturally;
2) presoma preparation 2.:
A) batch mixing mixes:
With Li
2CO
3And MnCO
3Ratio mixing and ball milling according to Li element, Mn element mol ratio 2:1;
B) presoma is processed:
The powder that step a) is obtained mixes, and 2. sintering 36h under 500 ℃ high temperature gets presoma;
3) 2. 1. presoma being mixed according to mol ratio 0.7:0.3 with presoma, is the HNO of 0.1mol/L with concentration
3Solution is processed;
4) the mixing presoma with the step 3) pickling processes is washed till neutrality with deionized water, and the rear spray drying that stirs obtains microspheroidal and mixes presoma;
5) 500 ℃ of sintering 10h of the mixing presoma that step 4) is made cross 300 mesh sieves after the cooling, obtain the lithium-rich manganese-based solid solution cathode material of microballoon stratiform, and molecular formula is 0.3Li
2MnO
30.7LiMn
0.5Ni
0.5O
2
The button electricity high temperature circulation curve of the lithium-rich manganese-based solid solution cathode material preparation of Comparative Examples, as shown in Figure 5.
Lithium-rich manganese-based solid solution cathode material electric property comparative analysis to embodiment 1-3 and Comparative Examples:
The lithium-rich manganese-based solid solution cathode material of embodiment 1～3 and Comparative Examples is made into 2032 type button cell test results, shown in table 1,2.
The measurement result of the battery that the lithium-rich manganese-based solid solution cathode material of table 1 embodiment 1～3 and Comparative Examples is made
The measurement result of the battery that the lithium-rich manganese-based solid solution cathode material of table 2 embodiment 1～3 and Comparative Examples is made
2032 type button cells of lithium-rich manganese-based solid solution cathode material preparation of the present invention, battery core discharges and recharges at 2.5～4.6V voltage range, charges and discharge first efficient and reaches more than 95%; 0.2C more than the discharge gram volume performance 209mAh/g.Battery has excellent cycle performance, and 0.5C charges and discharge 100 Capacitance reserves of circulation more than 90% under 2.5～4.3V, normal temperature; 300 Capacitance reserves of 55 ℃ of lower 0.5C circulations of high temperature are more than 80%; Discharge is more than 90% of 1C capacity under the 3C multiplying power.
The present invention has the following advantages:
1, reversible discharge capacity is higher and gram volume is higher first.
2, cycle performance is better under the normal temperature environment, and doped metal ion makes the structure of material more stable.
3, high rate performance is higher under the normal temperature environment.
4, cycle performance is more superior under the hot environment, prevents that effectively the structure of material from high temperature changing.
Claims (8)
1. the lithium-rich manganese-based solid solution cathode material of microballoon stratiform is characterized in that, the molecular formula of this material is xLi
2Mn
1-yN
yO
3(1-x) LiMn
1-zM
zO
2, M is one or both among Ni, the Co in the formula; N is one or more among Fe, Cr, Al, the Mg, 0＜x≤0.3,0＜y≤0.1,0＜z≤0.7.
2. the preparation method of the lithium-rich manganese-based solid solution cathode material of microballoon stratiform as claimed in claim 1 is characterized in that, step is as follows:
1) presoma preparation 1.:
A) preparation of solution:
Solution A: manganese source compound, M source compound according to manganese, M element mol ratio 1-z:z weighing, are added in the deionized water and make total concentration 1.0～4.0mol/L metal salt solution, and wherein M is one or both among Ni, the 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:
In reactor, add deionized water, bath temperature is 40～60 ℃, after passing into inert gas and making the reaction environment anaerobic, solution B and solution C are added in the reactor according to volume ratio 1:m, regulate pH value 8～12, rotating speed 100 ~ 200rpm, then pump into simultaneously solution A, solution B and solution C in the reactor, control manganese and the total ion of M metal and mol ratio hydroxy are 1:2, at 40～60 ℃ of lower insulations and the lasting 2 ~ 8h that stirs, the control pH is precipitated, wherein 1≤m≤1.5 10～12;
C) presoma is processed:
To precipitate Mn (OH)
2And M (OH)
2Filter, washing, 90～110 ℃ 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, ball milling mixes; With 450～550 ℃ of calcinings of mixture, 3～6h, be warming up to 850～950 ℃ of calcining 5～20h, 1. cooling obtains precursor naturally;
2) presoma preparation 2.:
A) with Li source compound, manganese source compound, the N element oxide ratio mixing and ball milling according to the mol ratio 2:1-y:y of Li element, Mn element, N element, wherein, N is one or more among Fe, Cr, Al, the Mg, 0＜y≤0.1;
B) presoma is processed:
The powder that step a) is obtained mixes, and 2. sintering 5～72h under 500～1000 ℃ high temperature gets presoma;
3) 2. 1. presoma being mixed according to mol ratio 1-x:x with presoma, is that the Acidwash solution of 0.1～0.3mol/L is processed with concentration, wherein, and 0＜x≤0.3;
4) the mixing presoma with the step 3) pickling processes is washed till neutrality with deionized water, and the rear spray drying that stirs obtains microspheroidal and mixes presoma;
5) 450～550 ℃ of sintering 3h～10h of the mixing presoma that step 4) is made cross 300 mesh sieves after the cooling, obtain the lithium-rich manganese-based solid solution cathode material xLi of microballoon stratiform
2Mn
1-yN
yO
3(1-x) LiMn
1-zM
zO
2
3. the preparation method of the lithium-rich manganese-based solid solution cathode material of a kind of microballoon stratiform according to claim 2 is characterized in that, described manganese source compound is at least a in manganese sulfate, manganese nitrate, manganese acetate, manganese carbonate or the manganese dioxide.
4. the preparation method of the lithium-rich manganese-based solid solution cathode material of a kind of microballoon stratiform according to claim 2 is characterized in that, described M source compound is at least a in nickelous sulfate, nickel nitrate, nickel acetate, cobaltous sulfate, cobalt nitrate or the cobalt acetate.
5. the preparation method of the lithium-rich manganese-based solid solution cathode material of a kind of microballoon stratiform according to claim 2 is characterized in that, described aqueous slkali is at least a in lithium hydroxide, NaOH or the potassium hydroxide.
6. the preparation method of the lithium-rich manganese-based solid solution cathode material of a kind of microballoon stratiform according to claim 2 is characterized in that, described Li source compound is at least a in lithium carbonate, lithium hydroxide or the lithium nitrate.
7. the preparation method of the lithium-rich manganese-based solid solution cathode material of a kind of microballoon stratiform according to claim 2 is characterized in that, described N element oxide is at least a in iron oxide, chromium oxide, aluminium oxide or the magnesium oxide.
8. the preparation method of the lithium-rich manganese-based solid solution cathode material of a kind of microballoon stratiform according to claim 2 is characterized in that, described Acidwash solution is at least a in nitric acid, sulfuric acid or the 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 true CN102916176A (en) | 2013-02-06 |
| CN102916176B 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) |
Cited By (15)
| 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 |
| CN106233513A (en) * | 2014-03-12 | 2016-12-14 | 株式会社Lg 化学 | Positive electrode active materials and the lithium secondary battery comprising it |
| CN108091858A (en) * | 2017-12-14 | 2018-05-29 | 桑顿新能源科技有限公司 | A kind of lithium-rich anode material of Li-O adulterated lithium manganate and preparation method thereof |
| CN108172823A (en) * | 2018-01-26 | 2018-06-15 | 浙江吉利汽车研究院有限公司 | Rich lithium manganese material, anode material for lithium-ion batteries, based lithium-ion battery positive plate, lithium ion battery and preparation method thereof |
| CN108448109A (en) * | 2018-03-23 | 2018-08-24 | 中南大学 | A kind of stratiform lithium-rich manganese-based anode material and preparation method thereof |
| CN108767229A (en) * | 2018-05-30 | 2018-11-06 | 天津巴莫科技股份有限公司 | Stepped combined rich oxidate for lithium solid-solution material of one kind 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 |
| CN112062167A (en) * | 2020-08-28 | 2020-12-11 | 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 |
| CN114455638A (en) * | 2021-12-28 | 2022-05-10 | 天津巴莫科技有限责任公司 | Solid electrolyte material with high lithium ion diffusivity and preparation method thereof |
| CN114804227A (en) * | 2022-04-24 | 2022-07-29 | 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 |
| CN118367149A (en) * | 2024-06-17 | 2024-07-19 | 深圳市德方创域新能源科技有限公司 | Lithium supplementing material, preparation method thereof, positive electrode material and secondary battery |
Citations (5)
| 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 |
| 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 |
| CN101707252A (en) * | 2009-11-09 | 2010-05-12 | 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 |
| CN101764222A (en) * | 2009-12-22 | 2010-06-30 | 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 (5)
| 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 |
| 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 |
| CN101707252A (en) * | 2009-11-09 | 2010-05-12 | 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 |
| CN101764222A (en) * | 2009-12-22 | 2010-06-30 | 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 |
Non-Patent Citations (1)
| Title |
|---|
| MITSUHARU TABUCHIA、YOKO NABESHIMA、TOMONARI TAKEUCHIA: "Fe content effects on electrochemical properties of Fe-substituted Li2MnO3 positive electrode material", 《JOURNAL OF POWER SOURCES》 * |
Cited By (22)
| 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 |
| CN106233513A (en) * | 2014-03-12 | 2016-12-14 | 株式会社Lg 化学 | Positive electrode active materials and the lithium secondary battery comprising it |
| US10128502B2 (en) | 2014-03-12 | 2018-11-13 | Lg Chem, Ltd. | Positive electrode active material and lithium secondary battery including the same |
| CN108091858A (en) * | 2017-12-14 | 2018-05-29 | 桑顿新能源科技有限公司 | A kind of lithium-rich anode material of Li-O adulterated lithium manganate and preparation method thereof |
| 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 |
| CN108172823A (en) * | 2018-01-26 | 2018-06-15 | 浙江吉利汽车研究院有限公司 | Rich lithium manganese material, anode material for lithium-ion batteries, based lithium-ion battery positive plate, lithium ion battery and preparation method thereof |
| CN108448109A (en) * | 2018-03-23 | 2018-08-24 | 中南大学 | A kind of stratiform lithium-rich manganese-based anode material and preparation method thereof |
| CN108767229A (en) * | 2018-05-30 | 2018-11-06 | 天津巴莫科技股份有限公司 | Stepped combined rich oxidate for lithium solid-solution material of one kind 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 |
| CN112062167A (en) * | 2020-08-28 | 2020-12-11 | 常熟理工学院 | Micron-sized binary doped lithium-rich material and preparation method and application thereof |
| 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 |
| CN114455638A (en) * | 2021-12-28 | 2022-05-10 | 天津巴莫科技有限责任公司 | Solid electrolyte material with high lithium ion diffusivity and preparation method thereof |
| 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 |
| CN114804227A (en) * | 2022-04-24 | 2022-07-29 | 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 |
| 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 |
| CN118367149A (en) * | 2024-06-17 | 2024-07-19 | 深圳市德方创域新能源科技有限公司 | Lithium supplementing material, preparation method thereof, positive electrode material and secondary battery |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102916176B (en) | 2015-06-17 |
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 | |
| CN102751480B (en) | A kind of cladded type lithium-rich manganese base material and preparation method thereof | |
| CN102074679B (en) | Method for preparing spherical aluminum-doped nickel lithium carbonate for lithium ion battery positive electrode material | |
| 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 | |
| CN102315429B (en) | The preparation method of aluminum-doped material of cathode of lithium ion battery with solid phase process | |
| CN102569780B (en) | Method for preparing lithium ion battery cathode material with layered structure | |
| CN102394297B (en) | Spherical compound lithium-rich multielement cathode material with core shell structure and preparation method thereof | |
| 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 | |
| CN102306751B (en) | The preparation method of wet-processed aluminium-coated lithium ion battery cathode material | |
| 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 | |
| CN102683645A (en) | Preparation method of layered lithium-rich manganese base oxide of positive material of lithium ion battery | |
| CN103715409A (en) | Method for preparing coated lithium ion battery cathode material of lithium nickel manganese oxide | |
| CN104966820A (en) | Lithium-ion battery precursor material, composite positive electrode material and preparation method thereof | |
| CN102916171B (en) | Concentration-gradually-changed spherical lithium nickel manganese oxide cathode material and preparation method thereof | |
| CN103647070B (en) | A kind of rare earth samarium is modified the preparation method of tertiary cathode material | |
| CN102838169B (en) | Preparation method of iron-containing lithium-rich manganese-based positive electrode material | |
| CN103413926B (en) | Preparation method of lithium nickel cobalt manganese oxide precursor | |
| CN102983326A (en) | Spherical lithium-nickel-cobalt composite oxide positive electrode material preparation method | |
| CN103972499A (en) | Modified nickel-cobalt lithium aluminate positive electrode material and preparation method thereof | |
| CN102730761A (en) | Oxalate coprecipitation preparation method for high-capacity lithium-rich cathode material | |
| CN102832387B (en) | Layer-structured ternary material with rich lithium and high manganese as well as preparation method and application 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 of 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 |