CN103570083B - A kind of preparation method of lithium ion battery anode material nickel cobalt aluminium spherical precursor - Google Patents
A kind of preparation method of lithium ion battery anode material nickel cobalt aluminium spherical precursor Download PDFInfo
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- CN103570083B CN103570083B CN201310504619.1A CN201310504619A CN103570083B CN 103570083 B CN103570083 B CN 103570083B CN 201310504619 A CN201310504619 A CN 201310504619A CN 103570083 B CN103570083 B CN 103570083B
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- 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 discloses a kind of preparation method of lithium ion battery anode material nickel cobalt aluminium spherical precursor, by water soluble nickel salt, cobalt salt and aluminium salt are dissolved into metal mixed saline solution, again by metal mixed saline solution, complexing agent aqueous solution, it is in 20 ~ 60 DEG C of reactors that the precipitation reagent aqueous solution is injected into temperature continuously through delicate flow control system respectively, control reaction system mixing speed, control reacting liquid pH value, sustained response generates precipitation, then press filtration, washing, again clean filter cake is distributed in distilled water, control solid-to-liquid ratio, be made into slurries, the slurries prepared are carried out spraying dry, control air intake, leaving air temp, nickel cobalt aluminium spherical precursor can be obtained.The present invention prepares the method for nickel cobalt aluminium spherical precursor, and technological process is simple, and reaction is easy to control, and product good sphericity, even particle size distribution, has vast potential for future development, and market potential is large.
Description
Technical field
The present invention relates to a kind of preparation technology of anode material for lithium-ion batteries, particularly a kind of preparation method of nickel cobalt aluminium spherical precursor, belongs to lithium ion secondary battery anode material technical field.
Background technology
Lithium ion battery, with its advantage such as high energy density, high discharge platform, is widely used in the portable electric appts such as mobile phone, camera, notebook computer.Along with the requirement of people to lithium ion battery is more and more higher, people need the lithium ion battery that service time is longer, size is less, weight is lighter, the performances such as fail safe is good, specific capacity is high, stable circulation that this just requires anode material for lithium-ion batteries to have concurrently, but cobalt acid lithium, LiMn2O4, LiFePO4 and nickel-cobalt-manganese ternary material ripe at present is all difficult to meet above-mentioned requirements simultaneously.And nickel cobalt lithium aluminate price is low, compacted density is high, and gram volume is high, and volume and capacity ratio, higher than cobalt acid lithium, is with a wide range of applications.
Current synthesis nickel cobalt lithium aluminate cathode material Li (Ni
xco
yal
z) O
2method mainly comprise solid phase method, coprecipitation and sol-gel process, solid phase method technique is simple, and cost is lower, but electrochemical stability is poor; Coprecipitation first prepares spherical hydroxide precursor in a kettle., then mix with lithium salts by proportioning, under high temperature, sinter solid phase reaction again to form, its technique is relatively simple, material capacity is high, good cycle, but sintering temperature is higher, and energy consumption is large: the material property of sol-gel process synthesis is unstable.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of environmental protection, has compared with high performance-price ratio and the preparation method of technique simple lithium ion battery anode material nickel cobalt aluminium spherical precursor, thus overcomes above-mentioned the deficiencies in the prior art.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows:
A preparation method for lithium ion battery anode material nickel cobalt aluminium spherical precursor, the method comprises the following steps:
(1), by water soluble nickel salt, cobalt salt and aluminium salt be dissolved into metal mixed saline solution, in metal mixed saline solution, nickel salt concentration is 0.4 ~ 1.2mol/L, and cobalt salt concentration is 0.075 ~ 0.225mol/L, and aluminium salinity is 0.025-0.075mol/L;
(2), above-mentioned metal mixed saline solution, complexing agent aqueous solution, the precipitation reagent aqueous solution being injected into temperature continuously through delicate flow control system is respectively in 20 ~ 60 DEG C of reactors, the mixing speed controlling reaction system is 100 ~ 250r/min, controlling reacting liquid pH value is 9.5 ~ 12.5, sustained response generates precipitation, then press filtration, washing, obtain the filter cake cleaned;
(3), be distributed in distilled water by above-mentioned clean filter cake, control solid-to-liquid ratio is 5:100 ~ 25:100, is made into slurries;
(4), by the above-mentioned slurries prepared carry out spraying dry, control that inlet temperature is 120 ~ 250 DEG C, leaving air temp is 90 ~ 200 DEG C, obtain nickel cobalt aluminium spherical precursor.
The preparation method of above-mentioned lithium ion battery anode material nickel cobalt aluminium spherical precursor, nickel salt described in step (1) is at least one in nickelous sulfate, nickel nitrate, nickel chloride; Described cobalt salt is at least one in cobaltous sulfate, cobalt nitrate, cobalt chloride; Described aluminium salt is at least one in aluminum sulfate, aluminum nitrate, aluminium chloride.
The preparation method of aforesaid lithium ion battery anode material nickel cobalt aluminium spherical precursor, described in step (2), complexing agent is ammoniacal liquor, and complexing agent concentration is 6.0 ~ 12.0mol/L; Described precipitation reagent can be NaOH and potassium hydroxide, also can be NaOH, or potassium hydroxide, and precipitant concentration is 1.0 ~ 3.0mol/L.
The preparation method of aforesaid lithium ion battery anode material nickel cobalt aluminium spherical precursor, the spheric granules D of the spherical nickel-cobalt aluminium presoma of preparation in step (4)
50(be also meso-position radius or median particle diameter, be commonly used to the particle mean size representing powder) is 10 ~ 15 μm.
Beneficial effect of the present invention: compared with prior art, the present invention adopts the coprecipitation-spray drying legal system of original creation to be ready for use on the spherical precursor of synthesis nickel cobalt lithium aluminate, the present invention adopts spraying dry, and by controlling drying process with atomizing condition, make aqueous solution rapid evaporation, dry formation particle size is homogeneous, spheric granules presoma, makes the nickel cobalt lithium aluminate material of follow-up preparation have the charge-discharge performance of stable homogeneous.The advantage of the method is: technological process is simple, and reaction is easy to control; Product good sphericity, even particle size distribution; Have vast potential for future development, market potential is large.
Compared with preparing spherical precursor with traditional employing coprecipitation, the present invention has following difference: (1), traditional coprecipitation directly obtain spherical precursor by coprecipitation process, coprecipitation process is the key obtaining spherical precursor, and the present invention is first co-precipitation, then obtain spherical precursor by spraying dry, spraying dry is the key obtaining spherical precursor.(2), traditional coprecipitation owing to being directly form spherical precursor, be the sphericity and the particle diameter that ensure presoma, need the strict process conditions controlling whole coprecipitation process, control difficulty large, complex technical process; Co-precipitation of the present invention is one of them processing step, the key forming spherical precursor is spraying dry instead of co-precipitation, so Coprecipitation of the present invention can control fairly simple, do not need strictly to control as traditional coprecipitation, process is fairly simple, is easy to control.
Compared with Chinese patent CN102969499A (a kind of preparation method of mono-disperse nickel, cobalt aluminium spherical precursor), both have following difference: (1) process route is different: the present invention adopts co-precipitation+drying process with atomizing route, and Chinese patent CN102969499A does not have co-precipitation, directly by Ultrasonic atomization method synthesis nickel cobalt aluminium spherical precursor.(2) precursor construction that obtains is different: what Chinese patent CN102969499A was obtained by ultrasonic atomizatio synthesis is nickel cobalt aluminum oxide presoma, be a kind of oxide, and the nickel cobalt aluminium presoma that the present invention obtains is a kind of hydroxide.(3) atomizing principles is different: the ultrasonic atomizatio of Chinese patent CN102969499A is a kind of spraying cracking technique, by ultrasonic atomizatio, original material is at high temperature decomposed, direct synthesis obtains nickel cobalt aluminium presoma, it is a chemical process, and spraying dry of the present invention is a simple physical process, the object of spraying is dried, and direct forming granulation, there is not building-up process.
Accompanying drawing explanation
Fig. 1 is the energy dispersion X ray spectrum figure of the embodiment of the present invention 1 preparing product;
Fig. 2 is 1000 times of scanning electron microscope (SEM) photographs of the embodiment of the present invention 1 preparing product;
Fig. 3 is 5000 times of scanning electron microscope (SEM) photographs of the embodiment of the present invention 1 preparing product;
Fig. 4 is the scanning X-ray diffraction spectrogram of the embodiment of the present invention 1 preparing product;
Fig. 5 is the grain size distribution of the embodiment of the present invention 1 preparing product.
Below in conjunction with the drawings and specific embodiments, the present invention is further illustrated.
Embodiment
Embodiment 1: appropriate nickelous sulfate, cobaltous sulfate and aluminium chloride are dissolved into metal mixed saline solution, in metal mixed saline solution, concentration of nickel sulfate is 0.4mol/L, and cobalt sulfate concentration is 0.075mol/L, and concentration of aluminum chloride is 0.025mol/L.Again above-mentioned metal mixed saline solution, complexing agent aqueous solution, the precipitation reagent aqueous solution being injected into temperature continuously through delicate flow control system is respectively in 20 ~ 60 DEG C of reactors, and complexing agent is wherein ammoniacal liquor, and complexing agent concentration is 6.0mol/L; Precipitation reagent is the mixed liquor of NaOH and potassium hydroxide, and precipitant concentration is 1.0mol/L; The mixing speed controlling reaction system is 100r/min, and controlling reacting liquid pH value is 11.0, and sustained response generates precipitation, and then press filtration, washing, obtain the filter cake cleaned; Be distributed in distilled water by clean filter cake again, control solid-to-liquid ratio is 5:100, is made into slurries, then the slurries prepared is carried out spraying dry, and control inlet temperature is 250 DEG C, leaving air temp is 120 DEG C, can obtain nickel cobalt aluminium spherical precursor, its spheric granules D
50it is 10 ~ 15 μm.
Embodiment 2: appropriate nickel nitrate, cobalt nitrate and aluminum nitrate are dissolved into metal mixed saline solution, in metal mixed saline solution, nickel nitrate concentration is 0.8mol/L, and cobalt nitrate concentration is 0.15mol/L, and aluminum nitrate concentration is 0.05mol/L.Again above-mentioned metal mixed saline solution, complexing agent aqueous solution, the precipitation reagent aqueous solution being injected into temperature continuously through delicate flow control system is respectively in 20 ~ 60 DEG C of reactors, and complexing agent is wherein ammoniacal liquor, and complexing agent concentration is 9mol/L; Precipitation reagent is NaOH, and precipitant concentration is 2mol/L; The mixing speed controlling reaction system is 180r/min, and controlling reacting liquid pH value is 11.0, and sustained response generates precipitation, and then press filtration, washing, obtain the filter cake cleaned; Be distributed in distilled water by clean filter cake again, control solid-to-liquid ratio is 15:100, is made into slurries, then the slurries prepared are carried out spraying dry, and control inlet temperature is 120 DEG C, leaving air temp is 90 DEG C, obtains nickel cobalt aluminium spherical precursor.
Embodiment 3: appropriate nickel chloride, cobalt chloride and aluminum nitrate are dissolved into metal mixed saline solution, in metal mixed saline solution, nickel chloride concentration is 1.2mol/L, and cobalt chloride concentration is 0.225mol/L, and aluminum nitrate concentration is 0.075mol/L.Again above-mentioned metal mixed saline solution, complexing agent aqueous solution, the precipitation reagent aqueous solution being injected into temperature continuously through delicate flow control system is respectively in 20 ~ 60 DEG C of reactors, and complexing agent is wherein ammoniacal liquor, and complexing agent concentration is 12mol/L; Precipitation reagent is potassium hydroxide, and precipitant concentration is 3mol/L; The mixing speed controlling reaction system is 250r/min, and controlling reacting liquid pH value is 11.0, and sustained response generates precipitation, and then press filtration, washing, obtain the filter cake cleaned; Be distributed in distilled water by clean filter cake again, control solid-to-liquid ratio is 25:100, is made into slurries, then the slurries prepared are carried out spraying dry, and control inlet temperature is 180 DEG C, leaving air temp is 120 DEG C, obtains nickel cobalt aluminium spherical precursor.
Embodiments of the present invention are not limited to above-described embodiment, and the various changes made under the prerequisite not departing from present inventive concept all belong within protection scope of the present invention.
Claims (3)
1. a preparation method for lithium ion battery anode material nickel cobalt aluminium spherical precursor, is characterized in that, comprises the following steps:
(1), by water soluble nickel salt, cobalt salt and aluminium salt be dissolved into metal mixed saline solution, in metal mixed saline solution, nickel salt concentration is 0.4 ~ 1.2mol/L, and cobalt salt concentration is 0.075 ~ 0.225mol/L, and aluminium salinity is 0.025-0.075mol/L;
(2), above-mentioned metal mixed saline solution, complexing agent aqueous solution, the precipitation reagent aqueous solution being injected into temperature continuously through delicate flow control system is respectively in 20 ~ 60 DEG C of reactors, the mixing speed controlling reaction system is 100 ~ 250r/min, controlling reacting liquid pH value is 9.5 ~ 12.5, sustained response generates precipitation, then press filtration, washing, obtain the filter cake cleaned;
(3), be distributed in distilled water by above-mentioned clean filter cake, controlling solid-to-liquid ratio is 5: 100 ~ 25: 100, is made into slurries;
(4), by the above-mentioned slurries prepared carry out spraying dry, control that inlet temperature is 250 DEG C, leaving air temp is 120 DEG C, nickel cobalt aluminium spherical precursor can be obtained, the spheric granules D of spherical nickel-cobalt aluminium presoma
50it is 10 ~ 15 μm.
2. the preparation method of lithium ion battery anode material nickel cobalt aluminium spherical precursor as claimed in claim 1, it is characterized in that, nickel salt described in step (1) is at least one in nickelous sulfate, nickel nitrate, nickel chloride; Described cobalt salt is at least one in cobaltous sulfate, cobalt nitrate, cobalt chloride; Described aluminium salt is at least one in aluminum sulfate, aluminum nitrate, aluminium chloride.
3. the preparation method of lithium ion battery anode material nickel cobalt aluminium spherical precursor as claimed in claim 1, it is characterized in that, described in step (2), complexing agent is ammoniacal liquor, and complexing agent concentration is 6.0 ~ 12.0mol/L; Described precipitation reagent is NaOH and/or potassium hydroxide, and precipitant concentration is 1.0 ~ 3.0mol/L.
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| EP3378835A1 (en) * | 2017-03-20 | 2018-09-26 | Optimum Battery Co., Ltd. | Method for preparing precursor of nickel-cobalt-aluminum ternary cathode material, cathode plate, and lithium ion battery |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105024065A (en) * | 2015-07-02 | 2015-11-04 | 电子科技大学 | Lithium ion battery cathode material and preparation method thereof |
| CN105140473A (en) * | 2015-07-23 | 2015-12-09 | 苏州迪思伏新能源科技有限公司 | Synthesis method for lithium-rich manganese-based layered oxide material of secondary lithium-ion spherical battery |
| CN107204423B (en) * | 2017-05-18 | 2020-06-09 | 山东玉皇新能源科技有限公司 | Preparation method and application of high-rate ternary cathode material |
| CN107611423A (en) * | 2017-08-28 | 2018-01-19 | 浙江新时代海创锂电科技有限公司 | A kind of preparation method of nickel-cobalt-manganese ternary presoma |
| CN108467069B (en) * | 2018-04-12 | 2020-02-07 | 安徽同心新材料科技有限公司 | Nickel-cobalt-aluminum ternary material precursor with extremely low impurity content and preparation process and application thereof |
| CN110364721A (en) * | 2019-07-30 | 2019-10-22 | 北方奥钛纳米技术有限公司 | Nickel cobalt manganese stuff and other stuff and preparation method thereof, nickle cobalt lithium manganate anode material for lithium-ion batteries and preparation method thereof and lithium ion battery |
| CN112652762B (en) * | 2020-12-21 | 2022-06-14 | 中科(马鞍山)新材料科创园有限公司 | Single-crystal-structure ternary lithium battery positive electrode precursor material and preparation method and application thereof |
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| AU2002100001A4 (en) * | 2002-01-02 | 2002-03-07 | Dou, Shi Xue | Method for production of spherical nickel hydroxide for rechargeable nickel-metal hydride batteries |
| CN100583512C (en) * | 2008-04-14 | 2010-01-20 | 天津巴莫科技股份有限公司 | Spherical aluminum-doped nickel cobalt lithium for lithium ion battery and its making method |
| CN102403501A (en) * | 2011-11-24 | 2012-04-04 | 上海电力学院 | Method for preparation of cathode material spherical FePO4 of lithium-ion battery |
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| EP3378835A1 (en) * | 2017-03-20 | 2018-09-26 | Optimum Battery Co., Ltd. | Method for preparing precursor of nickel-cobalt-aluminum ternary cathode material, cathode plate, and lithium ion battery |
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