CN103022456A - Preparation method of 5V high-voltage anode material for lithium battery - Google Patents
Preparation method of 5V high-voltage anode material for lithium battery Download PDFInfo
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- CN103022456A CN103022456A CN2012105362194A CN201210536219A CN103022456A CN 103022456 A CN103022456 A CN 103022456A CN 2012105362194 A CN2012105362194 A CN 2012105362194A CN 201210536219 A CN201210536219 A CN 201210536219A CN 103022456 A CN103022456 A CN 103022456A
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Abstract
The invention discloses a preparation method of a 5V high-voltage anode material for a lithium battery. The preparation method comprises the following steps of: preparing a solution by using nickel salt and manganese salt according to a stoichiometric ratio, dropping a sodium hydroxide solution under stirring, strictly controlling parameters such as the temperature, pH value, dropping speed, and stirring speed of the system, obtaining Ni-Mn hydroxide precipitates in which the ratio of Mn: Ni is 0.65: 0.35, leaching, washing and drying the precipitates, and mixing the precipitates with lithium salt according to a stoichiometric ratio; using a high-speed mixing granulator for pelleting the mixture, calcining the dried mixture particles under a nitrogen atmosphere according to certain procedures, and carrying out crushing grading after cooling to prepare the high-voltage anode material. The prepared Ni-Mn hydroxide is more ideal pure substance; and particles are uniformly distributed so that the structural stability of the material embedded in or taken off from a high-voltage region Li can be increased, thus the circulation performance of the anode material is improved.
Description
Technical field
The present invention relates to a kind of preparation method of 5V high voltage lithium electricity positive electrode, be used for anode material for lithium-ion batteries, belong to the new energy materials field.
Background technology
Lithium rechargeable battery has higher energy density with respect to other rechargeable batteries, and is so application is very extensive, little of various portable electric appts.All can use lithium ion battery to electric automobile greatly.As the positive electrode of lithium ion battery, must satisfy following requirement: have stable discharge platform, high energy density, high power density, excellent cycle performance, environmental friendliness, low price etc.But the positive electrodes that use in a large number at present are such as LiCoO
2, LiMn
2O
4, LiFePO
4All less than 4V, many cells if the acquisition high voltage need be connected just will cause safeguarding the problems such as inconvenient, that security performance is bad Deng discharge voltage plateau, so the exploitation preparation has high voltage and jumbo cell positive material seems particularly important.
In recent years for the high voltage investigation of materials more be LiNi
0.5Mn
1.5O
4, studies show that there is the platform about a 4.7V in it in the charge and discharge process, has good cycle performance and higher specific capacity (theoretical value 147mAh/g), can be used for the used for electric vehicle power-type lithium ion battery.LiNi
0.5Mn
1.5O
4Synthetic method have a lot, mainly contain high temperature solid-state method, coprecipitation, sol-gel process, molten salt growth method, ullrasonic spraying high-temperature decomposition etc.We have invented the high-voltage anode material of another proportioning on this basis.
Summary of the invention
For the deficiency that prior art exists, technical problem to be solved by this invention is, provides a kind of high voltage platform, high power capacity, second particle of obtaining to be the preparation method of spherical lithium electricity positive electrode.
For solving the problems of the technologies described above, the technical solution used in the present invention is: a kind of preparation method of 5V high-voltage lithium-battery cathode material may further comprise the steps:
Nickel salt and the manganese salt that (1), will measure ratio are mixed with solution, reaction temperature is located at 35～70 ℃, under the mixing speed of 50r/min～70r/min, splash in 0.2～3.0mol/L sodium hydroxide solution, pH value with the ammoniacal liquor regulation system, make it be controlled at 5.0～8.0, the parameters such as regulator solution rate of addition, mixing speed obtain spherical Ni-Mn precipitation of hydroxide;
(2), precipitation is dry after suction filtration, washing;
(3), dried presoma is carried out first ball milling mixings 0-5～2h with the lithium salts of metering ratio, carry out precision mixing 0.5～2h with high-speed mixing granulating machine again;
(4), the material adding additives that mixes is carried out granulation, then be placed on 100～220 ℃ of dryings in the drying box;
(5), with dried compound particles under nitrogen atmosphere by the calcining of 750～100 ℃ of insulation 12～22h programs, crushing and classification gets final positive electrode after the cooling.
The preparation method of above-mentioned 5V high-voltage lithium-battery cathode material, the Mn/Ni mol ratio is in the presoma of described positive electrode: 0.65: 0.35.
The preparation method of above-mentioned 5V high-voltage lithium-battery cathode material, used nickel salt is Ni (NO
3)
26H
2O, NiSO
46H
2O, NiCl
26H
2O, Ni (CH
3COO)
24H
2Among the O one or more; Used manganese salt is Mn (NO
3)
2, MnSO
4H
2O, MnCl
24H
2O, Mn (CH
3COO)
2H
2Among the O one or more.
The preparation method of above-mentioned 5V high-voltage lithium-battery cathode material, the pH value of described reaction system is 6.5, and temperature is 50 ℃, and mixing speed is 60r/min.
The preparation method of above-mentioned 5V high-voltage lithium-battery cathode material, described ball milling incorporation time is 0.5h, carries out accurate incorporation time 1h with high-speed mixing granulating machine.
The preparation method of above-mentioned 5V high-voltage lithium-battery cathode material, described sintering carries out under nitrogen atmosphere, and described sintering scheme is 1000 ℃, insulation 16h.
The preparation method of above-mentioned 5V high-voltage lithium-battery cathode material, used binding agent is PVA or water in the described granulation step.
The preparation method of above-mentioned 5V high-voltage lithium-battery cathode material, baking temperature is 200 ℃ after the described granulation.
The preparation method's of 5V high-voltage lithium-battery cathode material of the present invention advantage is: prepared Ni-Mn hydroxide is more satisfactory pure substance, even particle distribution can improve material and embed at high voltage region Li/structural stability when deviating from, thus improve the cycle performance of positive electrode.
Description of drawings
Fig. 1 is the SEM figure of high-voltage anode material;
Fig. 2 is the first charge-discharge curve chart of high-voltage anode material.
Embodiment
Below in conjunction with drawings and the specific embodiments the present invention is described in further details;
Embodiment 1:
Press Mn: Ni=0.65: 0.35 mol ratio is with NiSO
46H
2O, MnSO
4H
2O is mixed with mixed solution, under the mixing speed of 50r/min it is slowly splashed in the sodium hydroxide solution of 2.0mol/L, and the pH value with the ammoniacal liquor regulation system makes it be controlled at 6.5, and reaction temperature is located at 50 ℃ until reaction finishes to generate black precipitate.The suction filtration sediment washes with water 3 times, puts into 110 ℃ of dry presomas that get of baking oven.Take by weighing presoma 403g and mix with the 597g lithium carbonate, carry out first ball milling mixing 0.5h, carry out precision with high-speed mixing granulating machine again and mix 1h.The material adding additives PVA that mixes is carried out granulation, then be placed on 200 ℃ of dryings in the drying box.Dried compound particles is calcined by 1000 ℃ of insulation 16h programs under nitrogen atmosphere, and crushing and classification gets final positive electrode after the cooling.
The pattern of resulting materials is that class is spherical, does not have agglomeration between particle, and the first discharge specific capacity of material reaches 200mAh/g and sees Fig. 1, Fig. 2.
Embodiment 2:
Press Mn: Ni=0.65: 0.35 mol ratio is with NiSO
46H
2O, MnSO
4H
2O is mixed with mixed solution, under 60r/min stirs it is slowly splashed in the sodium hydroxide solution of 1.0mol/L, and the pH value with the ammoniacal liquor regulation system makes it be controlled at 7.0, and reaction temperature is located at 60 ℃ until reaction finishes to generate black precipitate.The suction filtration sediment washes with water 3 times, puts into 110 ℃ of dry presomas that get of baking oven.Take by weighing presoma 810g and mix with the 1194g lithium carbonate, carry out first ball milling mixing 1h, carry out precision with high-speed mixing granulating machine again and mix 1.5h.The material adding additives PVA that mixes is carried out granulation, then be placed on 200 ℃ of dryings in the drying box.Dried compound particles is calcined by 1100 ℃ of insulation 12h programs under nitrogen atmosphere, and crushing and classification gets final positive electrode after the annealing.
Embodiment 3:
Press Mn: Ni=0.65: 0.35 mol ratio is with Ni (NO
3)
26H
2O, MnCl
24H
2O is mixed with mixed solution, under 70r/min stirs it is slowly splashed in the sodium hydroxide solution of 3.0mol/L, and the pH value with the ammoniacal liquor regulation system makes it be controlled at 8.0, and reaction temperature is located at 70 ℃ until reaction finishes to generate black precipitate.The suction filtration sediment washes with water 3 times, puts into 110 ℃ of dry presomas that get of baking oven.Take by weighing presoma 1620g and mix with the 2388g lithium carbonate, carry out first ball milling mixing 2h, carry out precision with high-speed mixing granulating machine again and mix 2h.The material adding additives PVA that mixes is carried out granulation, then be placed on 200 ℃ of dryings in the drying box.Dried compound particles is calcined by 750 ℃ of insulation 22h programs under nitrogen atmosphere, and crushing and classification gets final positive electrode after the annealing.
Certainly, above-mentioned explanation is not to be limitation of the present invention, and the present invention also is not limited to above-mentioned giving an example; those skilled in the art; in essential scope of the present invention, the variation of making, remodeling, interpolation or replacement all should belong to protection scope of the present invention.
Claims (8)
1. the preparation method of a 5V high-voltage lithium-battery cathode material is characterized in that, may further comprise the steps:
Nickel salt and the manganese salt that (1), will measure ratio are mixed with solution, reaction temperature is located at 35～70 ℃, under the mixing speed of 50r/min～70r/min, splash in 0.2～3.0mol/L sodium hydroxide solution, pH value with the ammoniacal liquor regulation system, make it be controlled at 5.0～8.0, the parameters such as regulator solution rate of addition, mixing speed obtain spherical Ni-Mn precipitation of hydroxide;
(2), precipitation is dry after suction filtration, washing;
(3), the lithium salts of dried presoma with the metering ratio carried out first ball milling and mix 0.5～2h, carry out precision mixing 0.5～2h with high-speed mixing granulating machine again;
(4), the material adding additives that mixes is carried out granulation, then be placed on 100～220 ℃ of dryings in the drying box;
(5), with dried compound particles under nitrogen atmosphere by the calcining of 750～100 ℃ of insulation 12～22h programs, crushing and classification gets final positive electrode after the cooling.
2. the preparation method of 5V high-voltage lithium-battery cathode material according to claim 1, it is characterized in that: the Mn/Ni mol ratio is in the presoma of described positive electrode: 0.65: 0.35.
3. the preparation method of 5V high-voltage lithium-battery cathode material according to claim 2, it is characterized in that: used nickel salt is Ni (NO
3)
26H
2O, NiSO
46H
2O, NiCl
26H
2O, Ni (CH
3COO)
24H
2Among the O one or more; Used manganese salt is Mn (NO
3)
2, MnSO
4H
2O, MnCl
24H
2O, Mn (CH
3COO)
2H
2Among the O one or more.
4. the preparation method of 5V high-voltage lithium-battery cathode material according to claim 3, it is characterized in that: the pH value of described reaction system is 6.5, and temperature is 50 ℃, and mixing speed is 60r/min.
5. the preparation method of 5V high-voltage lithium-battery cathode material according to claim 3, it is characterized in that: described ball milling incorporation time is 0.5h, carries out accurate incorporation time 1h with high-speed mixing granulating machine.
6. the preparation method of 5V high-voltage lithium-battery cathode material according to claim 3, it is characterized in that: described sintering carries out under nitrogen atmosphere, and described sintering scheme is 1000 ℃, insulation 16h.
7. the preparation method of 5V high-voltage lithium-battery cathode material according to claim 3, it is characterized in that: used binding agent is PVA or water in the described granulation step.
8. the preparation method of 5V high-voltage lithium-battery cathode material according to claim 3 is characterized in that; Baking temperature is 200 ℃ after the described granulation.
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Cited By (1)
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|---|---|---|---|---|
| CN108269975A (en) * | 2016-12-30 | 2018-07-10 | 财团法人工业技术研究院 | High-voltage positive electrode material of lithium battery and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1595687A (en) * | 2003-09-08 | 2005-03-16 | 中国科学院物理研究所 | A positive electrode material for lithium secondary cell, and preparation and usage thereof |
| CN101465420A (en) * | 2009-01-09 | 2009-06-24 | 机械科学研究总院先进制造技术研究中心 | Method for preparing nickle lithium manganate material for lithium ion power battery anode |
| CN102751470A (en) * | 2011-04-18 | 2012-10-24 | 河南科隆集团有限公司 | Preparation method of lithium ion battery high-voltage composite cathode material |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1595687A (en) * | 2003-09-08 | 2005-03-16 | 中国科学院物理研究所 | A positive electrode material for lithium secondary cell, and preparation and usage thereof |
| CN101465420A (en) * | 2009-01-09 | 2009-06-24 | 机械科学研究总院先进制造技术研究中心 | Method for preparing nickle lithium manganate material for lithium ion power battery anode |
| CN102751470A (en) * | 2011-04-18 | 2012-10-24 | 河南科隆集团有限公司 | Preparation method of lithium ion battery high-voltage composite cathode material |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108269975A (en) * | 2016-12-30 | 2018-07-10 | 财团法人工业技术研究院 | High-voltage positive electrode material of lithium battery and preparation method thereof |
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Denomination of invention: Preparation method of 5V high-voltage anode material for lithium battery Effective date of registration: 20200629 Granted publication date: 20151125 Pledgee: China Construction Bank Corporation Qingdao Zhongshan Road sub branch Pledgor: QINGDAO QIANYUN HIGH-TECH NEW MATERIAL Co.,Ltd. Registration number: Y2020370010025 |
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