CN109148835A - The preparation method of alumina-coated nickel-cobalt lithium manganate cathode material - Google Patents
The preparation method of alumina-coated nickel-cobalt lithium manganate cathode material Download PDFInfo
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- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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Abstract
The present invention provides a kind of preparation method of alumina-coated nickel-cobalt lithium manganate cathode material, includes the following steps: dispersing agent and soluble meta-aluminic acid metal salt is soluble in water, formation meta-aluminic acid metal salt solution;Nickel cobalt manganese hydroxide is added into the meta-aluminic acid metal salt solution, adjusting pH using aqueous slkali is 8~13;Acid solution is added into the meta-aluminic acid metal salt solution, after pH reaches 7.5~10, stops that acid solution is added, through separation of solid and liquid, washing and drying, obtains aluminium hydroxide cladding nickel cobalt manganese hydroxide composite;Aluminium hydroxide cladding nickel cobalt manganese hydroxide composite is mixed with lithium salts, pressure oxidation calcining obtains alumina-coated nickel-cobalt lithium manganate cathode material.The preparation method process control, production cost is low, is suitable for industrialized production.
Description
Technical field
The present invention relates to battery material technical field more particularly to a kind of alumina-coated nickel-cobalt lithium manganate cathode materials
Preparation method.
Background technique
Lithium ion battery has high-energy density, has extended cycle life, the crowds such as memory-less effect as new generation of green material
More advantages, application field also constantly expands in recent years, and especially the fast development of electric car and demand constantly increase, and drives
The fast development of lithium ion battery.
It is special that the positive electrode of lithium ion battery will directly influence energy density performance possessed by lithium battery, specific power
Point, temperature feature and safety feature etc..In numerous positive electrodes, nickle cobalt lithium manganate tertiary cathode material have high capacity,
The advantages that good cycle performance and high rate performance is one of current most promising anode material for lithium-ion batteries.
However, ternary material (especially high-nickel material) has the shortcomings that some intrinsic, such as circulation generation under high voltages
Phase transformation causes that cyclical stability is poor, discharges O under high de- lithium state2Cause thermal stability difference etc..For these intrinsic disadvantages, to it
It is to improve one of the important means of tertiary cathode material performance that surface, which carries out coating modification,.Surface coating modification, i.e., in material table
Face forms cladding passivation layer, can prevent electrolyte from contacting with the direct of electrode material, inhibit the HF to dissociate in electrolyte to material
The dissolution of metal ion in material mitigates the destruction to positive electrode ontology, to improve the cycle performance and peace of lithium ion battery
Full performance.
Currently, cladding mode mainly has dry method cladding and wet process cladding.Dry method coats the hand for mostly using solid phase mechanical mixture
Coating and positive electrode are carried out simple mechanical mixture by section, and there are the non-uniform problems of clad for this technique.Wet process cladding
It is directly coated on positive electrode surface i.e. in aqueous systems or dicyandiamide solution, using modes such as physical bond or chemical depositions
Clad is formed, the dicyandiamide solution of this technique easily penetrates into inside positive electrode, so that it is generated some irreversible variations, to lead
Cause the decline of positive electrode performance.
Summary of the invention
In view of this, it is necessary to provide one kind to be evenly coated, process control, and improve the aluminium oxide of positive electrode performance
Coat the preparation method of nickel-cobalt lithium manganate cathode material.
The present invention provides a kind of preparation method of alumina-coated nickel-cobalt lithium manganate cathode material, includes the following steps:
Dispersing agent and soluble meta-aluminic acid metal salt is soluble in water, form meta-aluminic acid metal salt solution;
Nickel cobalt manganese hydroxide is added into the meta-aluminic acid metal salt solution, adjusting pH using aqueous slkali is 8~13;
Acid solution is added into the meta-aluminic acid metal salt solution, after pH reaches 7.5~10, stops that acid solution is added,
Through separation of solid and liquid, washing and drying, aluminium hydroxide cladding nickel cobalt manganese hydroxide composite is obtained;
Aluminium hydroxide cladding nickel cobalt manganese hydroxide composite is mixed with lithium salts, pressure oxidation calcining obtains oxygen
Change the nickel-cobalt lithium manganate cathode material of aluminium cladding.Wherein, the oxidation in the nickel-cobalt lithium manganate cathode material of the alumina-coated
Aluminium clad with a thickness of 2~30nm.
The preparation method of alumina-coated nickel-cobalt lithium manganate cathode material provided by the present invention is two using aluminium hydroxide
Property hydroxide this distinguishing feature, the introducing solubility meta-aluminic acid metal salt of innovation, aqueous solution, can be stable in alkalinity
It is dissolved in aqueous slkali, and is precipitated using acid solution, reaction process is slow and reaction speed uniform, controllable, will not generate a large amount of
Flocculence substance is deposited in nickel cobalt manganese hydroxide surfaces conducive to the nano-grade aluminum hydroxide particle in-situ of generation.
Also, the present invention is coated in nickel cobalt manganese hydroxide surfaces, high-temperature calcination is carried out after centrifugal drying, in this way
The most of moisture in material is eliminated before high-temperature calcination, avoids causing in high-temperature sintering process since moisture content is excessively high,
Material structure caused by the variation of atmosphere caused by moisture evaporates and moisture internal penetration destroys.It is different from the prior art after firing
Positive electrode surface handled, tertiary cathode material directly and contact with moisture, may cause moisture internal penetration and generate not
Reversible variation declines the performance of tertiary cathode material, and after tertiary cathode material surface is coated, is directly done
Dry no longer to carry out high-temperature calcination, dry not exclusively by generating, tertiary cathode material (especially high-nickel material) moisture content is excessively high,
The processing performance and chemical property for leading to battery are deteriorated.The present invention is while keeping core some materials performance, in material
Surface forms uniform clad, improves the security performance and cycle life of material.
The present invention is used only water, especially pure water as solvent and obtains oxygen by simple acid-base reaction and sintering processes
Change the nickel-cobalt lithium manganate cathode material of aluminium cladding, process control, production cost is low, is suitable for industrialized production.
Detailed description of the invention
Fig. 1 is the scanning electron microscope (SEM) photograph of the alumina-coated nickel-cobalt lithium manganate cathode material in the embodiment of the present invention 1.
Fig. 2 is the energy spectrum analysis figure of the alumina-coated nickel-cobalt lithium manganate cathode material in the embodiment of the present invention 1.
Fig. 3 is the X of the alumina-coated nickel-cobalt lithium manganate cathode material and commercially available nickle cobalt lithium manganate in the embodiment of the present invention 1
X ray diffraction comparison diagram.
Fig. 4 is alumina-coated nickel-cobalt lithium manganate cathode material and commercially available nickle cobalt lithium manganate in the embodiment of the present invention 1
Discharge curve for the first time.
Fig. 5 is alumina-coated nickel-cobalt lithium manganate cathode material and commercially available nickle cobalt lithium manganate in the embodiment of the present invention 1
Cycle performance figure.
Main element symbol description
Nothing
The present invention that the following detailed description will be further explained with reference to the above drawings.
Specific embodiment
The design of the present invention can use different form embodiment indicate, attached drawing shown in specification and text in illustrate be for
One of present invention implements example, and it is intended that the invention be not limited in shown attached drawing and/or described specific embodiment.
The present invention provides a kind of preparation method of alumina-coated nickel-cobalt lithium manganate cathode material, includes the following steps:
Dispersing agent and soluble meta-aluminic acid metal salt is soluble in water, form meta-aluminic acid metal salt solution;
Nickel cobalt manganese hydroxide is added into the meta-aluminic acid metal salt solution, adjusting pH using aqueous slkali is 8~13;
Acid solution is added into the meta-aluminic acid metal salt solution, after pH reaches 7.5~10, stops that acid solution is added,
Through separation of solid and liquid, washing and drying, aluminium hydroxide cladding nickel cobalt manganese hydroxide composite is obtained;
Aluminium hydroxide cladding nickel cobalt manganese hydroxide composite is mixed with lithium salts, pressure oxidation calcining obtains oxygen
Change aluminium and coats nickel-cobalt lithium manganate cathode material.Wherein, the aluminium oxide packet in the alumina-coated nickel-cobalt lithium manganate cathode material
Coating thickness is 2~30nm.
According to a particular embodiment of the invention, the mass ratio of the dispersing agent and water is 0.01%~5%, the solubility
The mass ratio of meta-aluminic acid metal salt and the nickel cobalt manganese hydroxide is 0.01%~30%, the nickel cobalt manganese hydroxide and water
Solid-to-liquid ratio be 1:1~1:8.
The mass ratio of dispersing agent and water that the present invention adds is 0.01%~5%, on the one hand can prevent aluminium hydroxide from existing
Reunite in generating process, forms flocculating setting, it on the other hand can also be in nickel cobalt manganese hydroxide substrate material surface shape
At adsorption layer, prevents to reunite between nickel cobalt manganese hydroxide precursor particle, keep system more uniform, guarantee aluminium hydroxide
Substrate material surface can be evenly coated at.
According to a particular embodiment of the invention, the reaction temperature that the preparation method carries out in the solution is 30~100 DEG C.
According to a particular embodiment of the invention, the soluble meta-aluminic acid metal salt includes potassium metaaluminate, sodium metaaluminate
At least one, the aqueous slkali includes at least one of sodium hydroxide, potassium hydroxide, ammonium hydroxide, ammonium hydrogen carbonate, the aqueous slkali
Mass concentration is 10%~40%.
According to a particular embodiment of the invention, the acid solution includes sulfuric acid, hydrochloric acid, nitric acid, carbonic acid, acetic acid, oxalic acid, lemon
At least one of lemon acid, the substance withdrawl syndrome of the acid solution are 0.01~5mol/L.
According to a particular embodiment of the invention, the dispersing agent and the soluble meta-aluminic acid metal salt are dissolved in the step of water
It further comprise that the pH of meta-aluminic acid metal salt solution is adjusted using the aqueous slkali 8~13 in rapid.
According to a particular embodiment of the invention, the dispersing agent includes polyvinyl alcohol, polyethylene glycol, sodium pyrophosphate, poly- third
At least one of olefin(e) acid.
According to a particular embodiment of the invention, the nickel cobalt manganese hydroxide with nickel, cobalt, manganese soluble salt aqueous solution, lead to
Cross the high nickel cobalt manganese hydroxide of coprecipitation preparation sphericity.
The coprecipitation is the method for the nickel cobalt manganese hydroxide of the known preparation of those skilled in the art.It is preferred that adopting
Coprecipitation reaction is carried out under the complexing of ammonia with the aqueous solution of nickel cobalt manganese soluble salt and sodium hydrate aqueous solution, prepares nickel cobalt manganese hydrogen
Oxide.
The soluble-salt of the nickel cobalt manganese includes at least one of nickel, cobalt, the sulfate of manganese, chlorate or nitrate.It is excellent
Choosing, the nickel, cobalt, manganese soluble-salt be nickel, cobalt, manganese sulfate.
In addition, nickel cobalt manganese hydroxide used in the present invention can also use commercially available product.
According to a particular embodiment of the invention, the acid solution is added into the meta-aluminic acid metal salt solution, when pH reaches
To after 7.5~10, further comprises and continue 20~80min of stirring.
According to a particular embodiment of the invention, the product after separation of solid and liquid is washed and is dried, the washing temperature
It is 25~100 DEG C, the drying temperature is 80~300 DEG C, the aluminium hydroxide cladding nickel cobalt manganese hydroxide obtained after the drying
The moisture content of object compound is 0.01%~3%.
According to a particular embodiment of the invention, the aluminium hydroxide cladding nickel cobalt manganese hydroxide composite is mixed with lithium salts
Mass ratio be 1:1~1:1.1, the temperature of pressure oxidation calcining is 600~1000 DEG C, and pressure is 0.1~5MPa, described
Calcination time is 5~15h.
Embodiment 1
(1) nickel cobalt manganese hydroxide is prepared
It is the sulfuric acid mixed salt solution that 5:2:3 prepares nickel, cobalt, manganese according to nickel, cobalt, manganese molar ratio, in 50 DEG C of insulation reactions
It is passed through nitrogen in kettle as protective atmosphere, sulfuric acid mixed salt solution, the hydrogen of nickel, cobalt, manganese is added with certain speed into reaction kettle
Sodium hydroxide solution and ammonium sulfate, control pH stable are stirred in 11, while by reaction kettle with the speed of 300r/min,
Generation coprecipitation reaction, the reaction time 15 hours.
Separate the sediment in the precipitation reaction, aged reaction, washing, drying, to obtain nickel cobalt manganese hydroxide.
Wherein, the ageing reaction uses the lye of 10wt%, and the ageing reaction temperature is 50 DEG C, and the ageing reaction time is
60min.The step of washing, specially uses pure water 8 times of 40 DEG C, and washing to the pH value of washing lotion is 9,150 DEG C of dryings
10 hours, the nickel cobalt manganese hydroxide is made.
(2) alumina-coated nickel-cobalt lithium manganate cathode material is prepared
According to the solid-to-liquid ratio of nickel cobalt manganese hydroxide and water 1:6, the pure water of 60kg, pure water temperature control are added into reaction kettle
System is at 70 DEG C.
According to proportional quantity, 12g dispersing agent polyethylene glycol is weighed respectively and 150g sodium metaaluminate is dissolved in pure water, wherein gathering
The mass ratio of ethylene glycol and pure water is 0.02%, and the mass ratio of sodium metaaluminate and nickel cobalt manganese hydroxide is 1.5%, sodium metaaluminate
Aqueous temperature is controlled at 70 DEG C.
After dissolution is sufficiently stirred in reaction kettle in polyethylene glycol and sodium metaaluminate, the hydrogen-oxygen for being 20% by using concentration
Change the aqueous solution pH of sodium solution control sodium metaaluminate 11.
After the pH value for regulating solution, weighed 10kg nickel cobalt manganese hydroxide is added in reaction kettle and is stirred point
It dissipates, at 70 DEG C, the sodium hydroxide solution for being 20% by using concentration controls pH value of solution 11 for solution temperature control in reaction kettle.
Concentration is added with the speed of 0.5L/h into reaction kettle to be reacted for the hydrochloric acid solution of 2mol/L, hydrochloric acid and inclined aluminium
Sour sodium, which carries out reaction, can make aluminium element be evenly distributed in the surface of nickel cobalt manganese hydroxide, to obtain sphericity height, aluminium
The nickel cobalt manganese hydroxide composite that element is evenly coated, temperature in the kettle control is at 70 DEG C in reaction process.
After pH value of solution reaches 7.5~10, stop that acid solution is added, continues to carry out after stirring 50min using centrifuge
It is separated by solid-liquid separation, washing and drying then is carried out to the material after centrifugation, washing temperature is 40 DEG C, and drying temperature is 150 DEG C, after dry
Moisture content in material is controlled 0.5%.
Then aluminium hydroxide nickel cobalt manganese hydroxide composite and lithium salts is coated to mix according to the molar ratio of 1:1.02
It closes, carries out pressure oxidation after mixing at 600 DEG C of temperature and 0.1MPa pressure and calcine 5h, obtain good sphericity, aluminium oxide packet
Cover uniform nickel-cobalt lithium manganate cathode material.
Referring to Fig. 1 scanning electron microscope (SEM) photograph, show the alumina-coated nickel cobalt lithium aluminate cathode material sphericity of embodiment preparation
Height, particle dispersion, epigranular.Energy spectrum analysis map referring to fig. 2 shows that the product surface of embodiment preparation has uniformly packet
The aluminium element covered, and measure the weight percent score that nickel element, manganese element, cobalt element, aluminium element account for ternary composite cathode material
It Wei 29.8%, 15.6%, 12.2% and 0.4%.By the nickle cobalt lithium manganate (NCM) of the alumina-coated of embodiment preparation and city
The nickle cobalt lithium manganate for selling uncoated aluminium oxide carries out X-ray diffraction analysis, from figure 3, it can be seen that the nickle cobalt lithium manganate of the two
Characteristic peak is fairly obvious, no dephasign peak.
By the nickel cobalt mangaic acid of the nickle cobalt lithium manganate (NCM) of the alumina-coated of embodiment preparation and commercially available uncoated aluminium oxide
Button cell made of lithium observes discharge scenario for the first time under room temperature.From fig. 4, it can be seen that the nickel cobalt mangaic acid through alumina-coated
Lithium first discharge specific capacity is significantly improved than the specific discharge capacity of the nickle cobalt lithium manganate of uncoated aluminium oxide.It is followed under observation room temperature
Ring performance.From fig. 5, it can be seen that nickel cobalt manganese of the nickle cobalt lithium manganate specific discharge capacity through alumina-coated than uncoated aluminium oxide
The specific discharge capacity of sour lithium is significantly improved.After circulation 100 times, capacity retention ratio is respectively 90.5% and 87.6%, illustrates oxygen
Its cycle performance is effectively promoted after changing aluminium cladding.
The above examples are only used to illustrate the technical scheme of the present invention and are not limiting, although referring to preferred embodiment to this hair
It is bright to be described in detail, those skilled in the art should understand that, it can modify to technical solution of the present invention
Or equivalent replacement, without departing from the spirit and scope of the technical solution of the present invention.
Claims (10)
1. a kind of preparation method of alumina-coated nickel-cobalt lithium manganate cathode material, which comprises the steps of:
Dispersing agent and soluble meta-aluminic acid metal salt is soluble in water, form meta-aluminic acid metal salt solution;
Nickel cobalt manganese hydroxide is added into the meta-aluminic acid metal salt solution, adjusting pH using aqueous slkali is 8~13;
Acid solution is added into the meta-aluminic acid metal salt solution, after pH reaches 7.5~10, stops that acid solution is added, through solid
Liquid separation, washing and drying obtain aluminium hydroxide cladding nickel cobalt manganese hydroxide composite;
Aluminium hydroxide cladding nickel cobalt manganese hydroxide composite is mixed with lithium salts, pressure oxidation calcining obtains aluminium oxide
Coat nickel-cobalt lithium manganate cathode material.
2. preparation method according to claim 1, which is characterized in that the mass ratio of the dispersing agent and water be 0.01%~
5%, the mass ratio of the soluble meta-aluminic acid metal salt and the nickel cobalt manganese hydroxide is 0.01%~30%, the nickel cobalt
The solid-to-liquid ratio of manganese hydroxide and water is 1:1~1:8.
3. preparation method according to claim 1, which is characterized in that the reaction temperature that the preparation method carries out in the solution
Degree is 30~100 DEG C.
4. preparation method according to claim 1, which is characterized in that the solubility meta-aluminic acid metal salt includes meta-aluminic acid
At least one of potassium, sodium metaaluminate, the aqueous slkali include sodium hydroxide, potassium hydroxide, ammonium hydroxide, ammonium hydrogen carbonate at least it
One, the mass concentration of the aqueous slkali is 10%~40%.
5. preparation method according to claim 1, which is characterized in that the acid solution includes sulfuric acid, hydrochloric acid, nitric acid, carbon
At least one of acid, acetic acid, oxalic acid, citric acid, the substance withdrawl syndrome of the acid solution are 0.01~5mol/L.
6. preparation method according to claim 1, which is characterized in that by the dispersing agent and the soluble meta-aluminic acid gold
Belong in the step of salt is dissolved in water, further includes adjusting the pH of the meta-aluminic acid metal salt solution using the aqueous slkali 8~13.
7. preparation method according to claim 1, which is characterized in that the dispersing agent include polyvinyl alcohol, polyethylene glycol,
At least one of sodium pyrophosphate, polyacrylic acid.
8. preparation method according to claim 1, which is characterized in that the acid solution is added to the meta-aluminic acid metal salt
It further include continuing 20~80min of stirring after pH reaches 7.5~10 in solution.
9. preparation method according to claim 1, which is characterized in that the product after separation of solid and liquid is washed and done
Dry, the washing temperature is 25~100 DEG C, and the drying temperature is 80~300 DEG C, the aluminium hydroxide packet obtained after the drying
The moisture content for covering nickel cobalt manganese hydroxide composite is 0.01%~3%.
10. preparation method according to claim 1, which is characterized in that the aluminium hydroxide coats nickel cobalt manganese hydroxide
The mass ratio that compound is mixed with lithium salts is 1:1~1:1.1, and the temperature of the pressure oxidation calcining is 600~1000 DEG C, pressure
For 0.1~5MPa, the calcination time is 5~15h.
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CN111092205B (en) * | 2019-12-19 | 2021-11-16 | 中冶瑞木新能源科技有限公司 | Core-double shell structure composite nickel-cobalt-manganese ternary precursor material and preparation method and application thereof |
CN112340786A (en) * | 2020-11-06 | 2021-02-09 | 惠州亿纬锂能股份有限公司 | Modification method of positive electrode material, modified positive electrode material and lithium ion battery |
CN112838208A (en) * | 2021-01-09 | 2021-05-25 | 厦门厦钨新能源材料股份有限公司 | Preparation method and application of lithium ion battery anode material |
CN112838208B (en) * | 2021-01-09 | 2023-09-12 | 厦门厦钨新能源材料股份有限公司 | Preparation method and application of lithium ion battery anode material |
CN114132951A (en) * | 2021-11-22 | 2022-03-04 | 广西银亿新材料有限公司 | Method for fluorine fixation and lithium extraction by pressure roasting of black powder of waste lithium battery |
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