CN101986441A - Method for preparing anode material for lithium ion batteries - Google Patents
Method for preparing anode material for lithium ion batteries Download PDFInfo
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- CN101986441A CN101986441A CN2009101090729A CN200910109072A CN101986441A CN 101986441 A CN101986441 A CN 101986441A CN 2009101090729 A CN2009101090729 A CN 2009101090729A CN 200910109072 A CN200910109072 A CN 200910109072A CN 101986441 A CN101986441 A CN 101986441A
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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
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- Y02E60/10—Energy storage using batteries
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Abstract
The invention belongs to the field of lithium ion batteries and discloses a method for preparing an anode material. The method comprises: ball-milling the precursor of the anode material in an atmosphere of sulfur dioxide; and sintering at high temperature in atmosphere of oxygen. In the method for preparing the anode material, the doping of the sulfur element is more uniform, the overall performance of the material is higher, and particularly the specific capacity and cycle index of the batteries are improved considerably. The method also has the characteristics of safety, reliability and no hidden danger.
Description
Technical field
The present invention relates to the lithium ion battery field, be specifically related to a kind of preparation method of anode material for lithium-ion batteries.
Background technology
Have document to point out: sulphur can significantly improve the charge-discharge performance of anode material for lithium-ion batteries.The mode of sintering for example mixes method, juice extractor mode of averaging etc. after the mechanical mixture commonly used at present.
The method that mixes promptly is to adopt magnetic stirring apparatus or mechanical agitation with positive electrode presoma and sulfate or sulfide mixing, this is owned by France in simple mechanical mixture, chemical reaction does not take place, and only could produce chemical reaction in follow-up calcining sulfur doping is entered.This method causes the local charge-discharge performance of positive electrode good, the phenomenon of partial error owing to can not make element sulphur in positive electrode the time is evenly mixed in calcining.
It is to adopt juice extractor to carry out powerful mechanical mixture that juice extractor mixes, and it is more even that this method ratio mixes method, but when dopant belongs to a small amount of or micro-, this method is lost mixed effect; The sulfur doping that very is not fit to positive electrode.
Summary of the invention
Technical problem to be solved by this invention is: in the prior art in the positive electrode element sulphur mix inhomogeneous, thereby provide a kind of uniform doping, the preparation method that the positive electrode performance is good.
A kind of method for preparing anode material of lithium-ion battery, it comprises: with positive electrode presoma ball milling under sulfur dioxide atmosphere; Then under oxygen atmosphere, high-temperature calcination.
Compared with prior art, the preparation method of positive electrode provided by the present invention utilizes ball milling with being doped in the positive electrode presoma of element sulphur, and it is more even to mix, the overall performance of material is superior, in battery specific capacity and cycle-index significant raising is arranged especially.This method also has safe and reliable, the characteristics of no hidden danger.
Embodiment
A kind of method for preparing anode material of lithium-ion battery, it comprises: with positive electrode presoma ball milling under sulfur dioxide atmosphere; Then under oxygen atmosphere, high-temperature calcination.
Wherein, positive electrode is a nickel manganese cobalt series positive electrode, for example unified compound (lithium cobalt oxygen, lithium nickel oxygen, lithium manganese oxygen), binary compound (Li-Ni-Mn-O, lithium cobalt manganese oxygen, lithium cobalt nickel oxygen), ternary compound (Li-Ni-Mn-Co-O) and to its derivative that mixes.
The positive electrode presoma is known in those skilled in the art, and its presoma is its corresponding hydroxide.LiCoO for example
2Presoma be LiCo (OH)
3, LiNi
0.8Co
0.2O
2Presoma be LiNi
0.8Co
0.2(OH)
3
The positive electrode presoma is joined in the ball grinder, feed inert gas or nitrogen and drive air in the ball grinder away, feed sulfur dioxide gas then to form sulfur dioxide atmosphere, ball milling;
Wherein, the D of positive electrode presoma
50Be preferably 8～15 μ m.
The amount that feeds sulfur dioxide is: the mol ratio of sulfur dioxide and positive electrode presoma is preferably 1: 233～and 1: 400, more preferably 1: 350.
Wherein, ball milling is operating as operation known in those skilled in the art.
Ball milling of the present invention can be roller ball mill, high-energy ball milling, planetary type ball-milling, preferred roller ball mill.
Wherein, the used abrading-ball of ball milling can be selected abrading-balls such as zirconium ball, agate ball, Ceramic Balls, the preferred zirconium ball of the present invention for use.
The present invention preferably adopts the abrading-ball of three kinds of different-diameters to come ball milling.
Wherein, the diameter of big ball is 2～4cm, and the diameter of middle ball is 1～1.9cm, and the diameter of bead is 0.1～0.5cm, and wherein the mass ratio of three kinds of abrading-balls is big ball: middle ball: bead=1: 3: 2.
During ball milling, the mass ratio of positive electrode presoma and abrading-ball is 1: 0.5～1: 2.
The rotating speed of ball milling is preferably 20～50r/s, preferred 2～5h of ball milling time.
The average grain diameter of positive electrode presoma is 1-3 μ m behind the ball milling.
To drop into through the positive electrode presoma of ball milling in the high-temperature calcination stove, under oxygen atmosphere, high-temperature calcination.
The oxygen atmosphere preferable flow rate is 0.5-10m
3The Oxygen Flow of/h.
Wherein, the high-temperature calcination operation also is operation known in those skilled in the art.The purpose of high-temperature calcination is to change the positive electrode presoma into positive electrode.
The present invention preferably includes the two-stage high-temperature calcination, and the phase I is calcined 8-12h down at 480-520 ℃, and second stage is calcined 20-30h down at 730-770 ℃.
The D of the positive electrode after the calcining
50Be 0.8～1.8 μ m.
The present invention adopts the reason of gas ball milling to be:
Gu adopt solid matter admittedly ball milling is the sulphur source, this method requires heavy dose of the doping, also very is not fit to the sulfur doping of positive electrode.
Liquid-solid mixed method generally adopts the glycerite of sodium sulphate, yet the impurity component that contains in the sodium sulphate can obviously reduce the performance of positive electrode, generally contains part nitric acid in the positive electrode presoma, and the adding of glycerine has certain danger.
The present invention adopts sulfur dioxide and positive electrode presoma ball milling, the positive electrode presoma is when ball milling, because abrading-ball collision with high-speed motion, produce a lot of reactive high active sites, very easily react with sulfur dioxide gas, go thereby uniformly element sulphur is doped in the positive electrode presoma, through follow-up high-temperature calcination, the overall performance of material is stable.
Method provided by the invention also has the good characteristics of particle surface form of the positive electrode of preparation.The present inventor thinks: particle is more little, and the energy that needs is just big more, when particle reaches certain particle diameter to a certain degree the time, just refinement again; When the present invention collides at the high speed ball milling, when making the activation of positive electrode presoma, under sulfur dioxide atmosphere, element sulphur is doped in the positive electrode presoma, make particle surface increase, energy reduces, and the secondary refinement takes place, and the reaction meeting is carried out towards optimal direction during refinement---the nodularization of particle; The secondary refinement makes part can't form the positive electrode presoma nodularization of spheric granules.
The invention will be further described below in conjunction with specific embodiment.
Embodiment 1
With positive electrode presoma LiNi
0.8Co
0.2(OH)
38kg puts into the ball grinder of roller ball grinding machine, and (abrading-ball is the big abrading-ball of 2cm for the 1.6Kg diameter, and the 4Kg diameter is the middle abrading-ball of 1cm to put into abrading-ball, 3.2Kg diameter is the little abrading-ball of 0.3cm), feed nitrogen, to get rid of the air in the ball grinder, feed the sulfur dioxide of 0.1mol then, ball milling.The control rotational speed of ball-mill is 30r/s, time 2.5h.
Taking out material and put into the high-temperature calcination stove, is 2m at oxygen gas flow rate
3In 500 ℃ of calcining 10h, calcine 20h for 750 ℃ again under the/h.
Make positive electrode A1.
Embodiment 2
Different is with embodiment 1: feed the sulfur dioxide of 0.2mol, other steps are with embodiment 1.Make positive electrode A2.
Embodiment 3
Different is with embodiment 1: feed the sulfur dioxide of 0.3mol, other steps are with embodiment 1.Make positive electrode A3.
Embodiment 4
Different is with embodiment 1: feed the sulfur dioxide of 0.4mol, other steps are with embodiment 1.Make positive electrode A4.
Embodiment 5
Different is with embodiment 1: feed the sulfur dioxide of 0.5mol, other steps are with embodiment 1.Make positive electrode A5.
Embodiment 6
As different from Example 3:, the rotating speed of ball milling is 10r/s, other parts are with embodiment 3.Make positive electrode A6.
Comparative Examples 1:
With positive electrode presoma LiNi
0.8Co
0.2(OH)
38kg puts into the ball grinder of roller ball grinding machine, and (abrading-ball is the big abrading-ball of 2cm for the 1.6Kg diameter, and the 4Kg diameter is the middle abrading-ball of 1cm to put into abrading-ball, 3.2Kg diameter is the little abrading-ball of 0.3cm), feed nitrogen,, add the Li of 0.1mol then to get rid of the air in the ball grinder
2SO
3, rotating speed is 30r/s, time 2.5h.
Taking out material and put into the pure oxygen atmosphere stove, is 2m at oxygen gas flow rate
3In 500 ℃ of calcining 10h, calcine 20h for 750 ℃ again under the/h.
Make positive electrode D1.
Comparative Examples 2:
Different is with embodiment: feed the sulfur dioxide (promptly not feeding sulfur dioxide) of 0mol, other steps are with embodiment 1.Make positive electrode D2.
Test performance:
The preparation of test battery:
(1) preparation of positive plate: is to be dissolved in N-methyl pyrrolidone at 100: 4: 5 positive electrode, acetylene black and PVDF with weight ratio, be coated in after stirring on the aluminium foil, baking, temperature is 100 ± 5 ℃, use tablet press machine to roll certain thickness, rolling cut becomes positive plate.
(2) preparation of negative plate: is to be dissolved in N-methyl pyrrolidone at 100: 3: 6 graphite, acetylene black and PVDF with weight ratio, be coated in after stirring on the Copper Foil, baking, temperature is 100 ± 5 ℃, use tablet press machine to roll certain thickness, rolling cut becomes negative plate.
(3) above-mentioned positive and negative electrode pole piece and 20 μ m are thick polypropylene diaphragm is wound into rectangular lithium ion battery electricity core, place in battery case and weld, subsequently, inject 1.0mol/LLiPF6/ (EC+EMC+DMC) (wherein EC, EMC and DMC mass ratio are 1: 1: 1) electrolyte, test battery is made in sealing.
The specific capacity test:
At room temperature, earlier with the 1.0mA constant current charge,, at the 4.2V constant voltage charge,, shelve 5min, with the 1.0mA constant-current discharge by electric current 0.1mA by voltage 4.2V.Calculate its specific capacity.The results are shown in Table 1.
The cycle performance test:
At room temperature, earlier with the 0.8mA constant current charge,, at the 4.2V constant voltage charge,, shelve 5min, with the 0.8mA constant-current discharge by electric current 0.06mA by voltage 4.2V.Repeat 500 times, calculate 500 times capability retention.The results are shown in Table 1.
Table 1
As can be seen from Table 1, the specific capacity and the circulation volume conservation rate of the positive electrode prepared of method provided by the present invention all are greatly improved.
Claims (10)
1. the preparation method of an anode material for lithium-ion batteries, it comprises: with positive electrode presoma ball milling under sulfur dioxide atmosphere; Then under oxygen atmosphere, high-temperature calcination.
2. the preparation method of anode material for lithium-ion batteries according to claim 1, it is characterized in that: the mol ratio of described sulfur dioxide and positive electrode presoma is 1: 233～1: 400.
3. the preparation method of anode material for lithium-ion batteries according to claim 2, it is characterized in that: the mol ratio of described sulfur dioxide and positive electrode presoma is 1: 350.
4. the preparation method of anode material for lithium-ion batteries according to claim 1 is characterized in that: the median particle diameter D of described anodal presoma
50Be 8～15 μ m.
5. the preparation method of anode material for lithium-ion batteries according to claim 1, it is characterized in that: the time of described ball milling is 2～3 hours.
6. the preparation method of anode material for lithium-ion batteries according to claim 1, it is characterized in that: the rotating speed of described ball milling is 20～50r/s.
7. the preparation method of anode material for lithium-ion batteries according to claim 1, it is characterized in that: the used abrading-ball of described ball milling comprises the abrading-ball of three kinds of different-grain diameters.
8. the preparation method of anode material for lithium-ion batteries according to claim 7, it is characterized in that: described abrading-ball comprises that diameter is that the big ball of 2～4cm, middle ball, the diameter that diameter is 1～1.9cm are the bead of 0.1～0.5cm, and the mass ratio of three kinds of abrading-balls is big ball: middle ball: bead=1: 3: 2.
9. the preparation method of anode material for lithium-ion batteries according to claim 7, it is characterized in that: the mass ratio of described positive electrode presoma and described abrading-ball is 1: 0.5～1: 2.
10. the preparation method of anode material for lithium-ion batteries according to claim 1 is characterized in that: described high-temperature calcination comprises the two-stage calcining, and the phase I is at 480～520 ℃ of calcining 8～12h down, and second stage is at 730～770 ℃ of calcining 20～30h down.
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| CN2009101090729A CN101986441B (en) | 2009-07-29 | 2009-07-29 | Method for preparing anode material for lithium ion batteries |
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|---|---|---|---|
| CN2009101090729A CN101986441B (en) | 2009-07-29 | 2009-07-29 | Method for preparing anode material for lithium ion batteries |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110831901A (en) * | 2017-06-28 | 2020-02-21 | 巴斯夫欧洲公司 | Method for preparing positive active material of lithium ion battery |
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|---|---|---|---|---|
| US5674645A (en) * | 1996-09-06 | 1997-10-07 | Bell Communications Research, Inc. | Lithium manganese oxy-fluorides for li-ion rechargeable battery electrodes |
| CN1332878C (en) * | 2005-10-11 | 2007-08-22 | 清华大学 | Prepn process of oxygen place doped lithium ferric phosphate powder |
| CN101339994B (en) * | 2008-09-01 | 2010-12-01 | 甘肃大象能源科技有限公司 | Preparation of multi-position doped lithium iron phosphate positive electrode material and application thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110831901A (en) * | 2017-06-28 | 2020-02-21 | 巴斯夫欧洲公司 | Method for preparing positive active material of lithium ion battery |
| US11862784B2 (en) | 2017-06-28 | 2024-01-02 | Basf Se | Process for making a cathode active material for a lithium ion battery |
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Inventor after: Chen Xiao Inventor before: Li Yang Inventor before: Xian Xuefeng |
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Effective date of registration: 20170317 Address after: Yang Lake Road 243000 in Anhui Province, Ma'anshan City Economic and Technological Development Zone Mazhi win rich science and Technology Park 9 Patentee after: Ma'anshan vigor Electric Technology Co., Ltd. Patentee after: Chen Xiao Address before: 518118 Pingshan Road, Pingshan Town, Shenzhen, Guangdong, No. 3001, No. Patentee before: Biyadi Co., Ltd. |
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