CN102403494A - Manganese-based layered crystal structure lithium battery anode material and preparation method thereof - Google Patents
Manganese-based layered crystal structure lithium battery anode material and preparation method thereof Download PDFInfo
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- CN102403494A CN102403494A CN2011103145244A CN201110314524A CN102403494A CN 102403494 A CN102403494 A CN 102403494A CN 2011103145244 A CN2011103145244 A CN 2011103145244A CN 201110314524 A CN201110314524 A CN 201110314524A CN 102403494 A CN102403494 A CN 102403494A
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- crystal structure
- anode material
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- manganese
- lithium
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- 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
Abstract
The invention relates to a manufacture technology of a lithium ion battery anode material, in particular to a manganese-based layered crystal structure lithium battery anode material and a preparation method thereof. The manganese-based layered crystal structure lithium battery anode material has a chemical formula of Li[Li0.20Ni0.133Co0.133Mn0.534]O2-aFa, wherein a is not less than 0.002 and not more than 0.02. According to the anode material and the preparation method thereof provided by the invention, low-cost metal magnesium is used for replacing most of cobalt in lithium cobaltite, raw materials have lower cost and a preparation process is simple, and micron-level powder particles can express excellent battery performances. The anode material has a capacity of reaching 220mAh/g which is about 50 percent of the capacity of lithium cobaltite and lithium iron phosphate, and has excellent battery performance. Through tests, under a 1C discharge multiplying power, with 100 charge cycles, about 95 percent of initial capacity is kept; meanwhile, under the condition of oversized current (exceeding 10C multiplying power) discharge, experiments prove that no fire and explosion exists, and excellent safety property is obtained.
Description
Technical field
The present invention relates to the manufacturing technology of anode material for lithium-ion batteries, specifically is a kind of lithium battery cathode material with manganese-based layered-crystal structure and preparation method thereof.
Background technology
Anode material of lithium battery commonly used in the market mainly contains three kinds: cobalt acid lithium (LiCoO
2), LiMn2O4 (LiMn
2O
4) and LiFePO4 (LiFePO
4).
Cobalt acid lithium (LiCoO
2) have layered crystal mechanism, the about 140mAh/g of accumulate capacity, cycle performance is more superior, but in the expensive price owing to the raw material cobalt, its application is confined to small-capacity cells, for example the rechargeable battery of small-sized electronic product.
LiMn2O4 (LiMn
2O
4), having spinel crystal structure, the cost of raw material is lower, but its capacity has only 100mAh/g, than cobalt acid lithium low about 40%.And its cycle performance is greater than 50
0(Electric power car operating temperature) can weaken greatly under the higher temperature of C, so preferred material that neither following Electric power car.
LiFePO4 (LiFePO
4), having olivine crystal structure, capacity is about 150mAh/g.Its cost of raw material is lower, but because of its preparation technology is extremely complicated, final finished electrode material price is still than higher.LiFePO4 is because the non-constant of its conductance; The powder particle that need process Nano grade just can show reasonable cycle performance of battery; This is just to causing very big difficulty on the preparation technology; Domestic have some producers attempting production, but because of its batch quality instability, can not go into operation on a large scale always.
Summary of the invention
Technical problem to be solved by this invention provides lithium battery cathode material with manganese-based layered-crystal structure that a kind of cost of raw material is low, preparation technology is simple, capacity is high and preparation method thereof.
The chemical formula of lithium battery cathode material with manganese-based layered-crystal structure of the present invention is: Li [Li
0.20Ni
0.133Co
0.133Mn
0.534] O
2-aF
a, 0.002≤a≤0.02 wherein.
The preparation method of above-mentioned material of the present invention is:
Step 1, spherical (Ni
x Co
y Mn
z ) (OH)
2(x:y:z=0.133:0.133:0.534) preparation of presoma may further comprise the steps:
1) with NiSO4, CoSO4, MnSO4 example in molar ratio are made into the aqueous solution, cation molar concentration rate Ni:Co:Mn=0.133:0.133:0.534, and the concentration summation of final all positive ions is 2.0 mol;
The above-mentioned metal ion solution that 2) will dispose adds in the stirred reactor of nitrogen atmosphere, and the blender mixing speed is 1000rpm, and heating and temperature control is at 60 ℃;
3) be that the NaOH solution of 2.0 mol splashes in the blender very slowly with concentration, to produce (Ni
0.166Co
0.166Mn
0.688) (OH)
2The deposition of particle; When splashing into the NaOH aqueous solution, slowly splash into the ammoniacal liquor that concentration is 4.0 mol; Splash into the speed of NaOH solution and ammoniacal liquor, should control with pH meter and ammonium ion densimeter, in entire reaction course, the pH value of reaction solution is controlled at 11.0, NH in the blender
3+Concentration be controlled at 0.36 mol;
4) after reaction finishes, with (the Ni that precipitates
0.166Co
0.166Mn
0.668) (OH)
2Granular product filters out and 110 ℃ of dryings, obtains graininess (Ni
0.166Co
0.166Mn
0.668) (OH)
2Presoma;
Step 2, high temperature solid-state method prepare layered crystal structure Li [Li
0.20Ni
0.133Co
0.133Mn
0.534] O
2-aF
a, may further comprise the steps:
1). with step 1 resulting granules shape (Ni
0.166Co
0.166Mn
0.668) (OH)
2Presoma is with LiOHH
2The O powder evenly mixes to get up, and the mixing molar ratio is Li
+: metal ion summation=1.3: 0.8;
2). mixed-powder is placed the sintering furnace of air atmosphere, earlier 480
0C heating 5 hours; Mix mixture 950 then with lithium fluoride
0C got final product to such an extent that have [a Li to layered crystal structure Li in air in sintering 10-20 hour
0.20Ni
0.133Co
0.133Mn
0.534] O
2-aF
a, 0.002≤a≤0.02 wherein.
Positive electrode of the present invention and preparation method thereof substitutes the most cobalts in the cobalt acid lithium with more cheap manganese metal, and the cost of raw material is lower, and preparation technology is simple, and the powder particle of micron level can show remarkable battery performance.The capacity of this positive electrode is up to 220mAh/g, and the capacity that leaves than cobalt acid lithium and LiFePO4 is high by about 50%.Its battery performance is remarkable, through test, under the 1C discharge-rate; Through 100 charging cycle, also possess about 95% of initial capacity, and; Under super-large current (surpassing the 10C multiplying power) discharge scenario, test no any catching fire and explosion phenomenon, prove the security performance that it is remarkable.
Embodiment
Embodiment:
Adopt co-electrodeposition method to combine high temperature solid-state method to prepare lithium battery cathode material with manganese-based layered-crystal structure, step is following:
One: spherical (Ni
x Co
y Mn
z ) (OH)
2(x:y:z=0.133:0.133:0.534) preparation of presoma.
1). with NiSO4, CoSO4, MnSO4 example in molar ratio are made into the aqueous solution, cation molar concentration rate Ni:Co:Mn=0.133:0.133:0.534, the concentration summation of final all positive ions is 2.0 mol.
2). NaOH is made into the aqueous solution of 2.0 mol
3). compound concentration is the ammoniacal liquor (NH of 4.0 mol
4OH)
4). get in the stirred reactor of the 2.0 liters of metal ion solutions that disposed adding nitrogen atmospheres, the blender mixing speed is 1000rpm, and heating and temperature are controlled at 60
0C,
5). with total amount is the NaOH solution that 4.2 liters of concentration are 2.0 mol
Very slowSplash in the blender, to produce (Ni
0.166Co
0.166Mn
0.688) (OH)
2The deposition of particle, whole splashing into the about 12-40 of process need hour; When splashing into the NaOH aqueous solution, slowly splash into the ammoniacal liquor that concentration is 4.0 mol, because ammoniacal liquor just is used for doing chelating agent, not consumptive raw material, so the speed that ammoniacal liquor splashes into should be slow more originally.
6). splash into the speed of NaOH solution and ammoniacal liquor, should control with pH meter and ammonium ion densimeter, in entire reaction course, the pH value of reaction solution is controlled at 11.0, NH in the blender
3+Concentration be controlled at 0.36 mol.
8). after reaction finishes, the total amount that precipitates is about 4.0 moles (Ni
0.166Co
0.166Mn
0.668) (OH)
2Granular product filters out and 110
0Dry about C.Resulting granules shape (Ni
0.166Co
0.166Mn
0.668) (OH)
2Presoma is about the about 5mm of their diameter.
Two: high temperature solid-state method prepares layered crystal structure Li [Li
0.20Ni
0.133Co
0.133Mn
0.534] O
2-aF
a
1). with front resulting granules shape (Ni
0.166Co
0.166Mn
0.668) (OH)
2Presoma is with LiOHH
2The O powder evenly mixes to get up.The mixing molar ratio is Li
+: metal ion summation=1.3: 0.8.The ratio here is greater than Li [Li
0.20Ni
0.133Co
0.133Mn
0.534] O
2In theoretical value (1.2:0.8).Using excessive lithium, is because the sub-fraction lithium can vapor away in sintering process.
2). top mixed-powder is placed the sintering furnace of air atmosphere, earlier 480
0C heating 5 hours; Mix mixture 950 then with lithium fluoride
0C got final product to such an extent that have [a Li to layered crystal structure Li in air in sintering 10-20 hour
0.20Ni
0.133Co
0.133Mn
0.534] O
2-aF
a, 0.002≤a≤0.02 wherein.The particle shape of end product is with the resulting presoma (Ni of the first step
0.166Co
0.166Mn
0.668) (OH)
2Particle shape very similar.
Claims (2)
1. lithium battery cathode material with manganese-based layered-crystal structure, it is characterized in that: its chemical formula is: Li [Li
0.20Ni
0.133Co
0.133Mn
0.534] O
2-aF
a, 0.002≤a≤0.02 wherein.
2. the preparation method of a lithium battery cathode material with manganese-based layered-crystal structure is characterized in that:
Step 1, spherical (Ni
x Co
y Mn
z ) (OH)
2(x:y:z=0.133:0.133:0.534) preparation of presoma may further comprise the steps:
1) with NiSO4, CoSO4, MnSO4 example in molar ratio are made into the aqueous solution, cation molar concentration rate Ni:Co:Mn=0.133:0.133:0.534, and the concentration summation of final all positive ions is 2.0 mol;
The above-mentioned metal ion solution that 2) will dispose adds in the stirred reactor of nitrogen atmosphere, and the blender mixing speed is 1000rpm, and heating and temperature control is at 60 ℃;
3) be that the NaOH solution of 2.0 mol splashes in the blender very slowly with concentration, to produce (Ni
0.166Co
0.166Mn
0.688) (OH)
2The deposition of particle; When splashing into the NaOH aqueous solution, slowly splash into the ammoniacal liquor that concentration is 4.0 mol; Splash into the speed of NaOH solution and ammoniacal liquor, should control with pH meter and ammonium ion densimeter, in entire reaction course, the pH value of reaction solution is controlled at 11.0, NH in the blender
3+Concentration be controlled at 0.36 mol;
4) after reaction finishes, with (the Ni that precipitates
0.166Co
0.166Mn
0.668) (OH)
2Granular product filters out and 110 ℃ of dryings, obtains graininess (Ni
0.166Co
0.166Mn
0.668) (OH)
2Presoma;
Step 2, high temperature solid-state method prepare layered crystal structure Li [Li
0.20Ni
0.133Co
0.133Mn
0.534] O
2-aF
a, may further comprise the steps:
1). with step 1 resulting granules shape (Ni
0.166Co
0.166Mn
0.668) (OH)
2Presoma is with LiOHH
2The O powder evenly mixes to get up, and the mixing molar ratio is Li
+: metal ion summation=1.3: 0.8;
2). mixed-powder is placed the sintering furnace of air atmosphere, earlier 480
0C heating 5 hours; Mix mixture 950 then with lithium fluoride
0C got final product to such an extent that have [a Li to layered crystal structure Li in air in sintering 10-20 hour
0.20Ni
0.133Co
0.133Mn
0.534] O
2-aF
a, 0.002≤a≤0.02 wherein.
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|---|---|---|---|
| CN2011103145244A CN102403494A (en) | 2011-10-17 | 2011-10-17 | Manganese-based layered crystal structure lithium battery anode material and preparation method thereof |
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ID=45885473
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104733732A (en) * | 2015-02-11 | 2015-06-24 | 江苏科捷锂电池有限公司 | Preparation method for F-substituted 523 ternary material |
| CN105280911A (en) * | 2014-07-22 | 2016-01-27 | 丰田自动车株式会社 | Positive active material for lithium-ion secondary battery, positive electrode for lithium-ion secondary battery, and lithium-ion secondary battery |
Citations (2)
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|---|---|---|---|---|
| CN101740773A (en) * | 2009-12-22 | 2010-06-16 | 江苏环能通环保科技有限公司 | Lithium battery cathode material with manganese-based layered-crystal structure and preparation method thereof |
| CN102171868A (en) * | 2008-09-30 | 2011-08-31 | 安维亚系统公司 | Fluorine doped lithium rich metal oxide positive electrode battery materials with high specific capacity and corresponding batteries |
-
2011
- 2011-10-17 CN CN2011103145244A patent/CN102403494A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102171868A (en) * | 2008-09-30 | 2011-08-31 | 安维亚系统公司 | Fluorine doped lithium rich metal oxide positive electrode battery materials with high specific capacity and corresponding batteries |
| CN101740773A (en) * | 2009-12-22 | 2010-06-16 | 江苏环能通环保科技有限公司 | Lithium battery cathode material with manganese-based layered-crystal structure and preparation method thereof |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105280911A (en) * | 2014-07-22 | 2016-01-27 | 丰田自动车株式会社 | Positive active material for lithium-ion secondary battery, positive electrode for lithium-ion secondary battery, and lithium-ion secondary battery |
| US10340513B2 (en) | 2014-07-22 | 2019-07-02 | Toyota Jidosha Kabushiki Kaisha | Positive active material for lithium-ion secondary battery, positive electrode for lithium-ion secondary battery, and lithium-ion secondary battery |
| CN104733732A (en) * | 2015-02-11 | 2015-06-24 | 江苏科捷锂电池有限公司 | Preparation method for F-substituted 523 ternary material |
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Application publication date: 20120404 |