CN105098165A - Preparation method of magnesium nickel cobalt aluminum oxide for lithium ion power battery and product thereof - Google Patents
Preparation method of magnesium nickel cobalt aluminum oxide for lithium ion power battery and product thereof Download PDFInfo
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- CN105098165A CN105098165A CN201510395930.6A CN201510395930A CN105098165A CN 105098165 A CN105098165 A CN 105098165A CN 201510395930 A CN201510395930 A CN 201510395930A CN 105098165 A CN105098165 A CN 105098165A
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- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/523—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron for non-aqueous cells
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2220/00—Batteries for particular applications
- H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
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Abstract
The invention relates to a preparation method of a magnesium nickel cobalt aluminum oxide for a lithium ion power battery. The magnesium nickel cobalt aluminum oxide is prepared according to a co-precipitation method. The preparation method comprises the following steps of: (1) reaction solution preparation; (2) precipitation reaction; (3) impurity removal; (4) drying; and (5) reconstruction and curing; a certain molar concentration of a nickel salt, a cobalt salt, a magnesium salt and an aluminum acid salt are matched according to a certain proportion, chemical precipitation reaction is carried out in a non-magnetic reaction kettle compatible with high radial cutting force and axial turbulence and provided with a multi-dimensional moving system resistant to flow in conditions of a certain temperature, flow quantity, PH value, stirring speed and the like and in mixture system existing with a chelating agent and a system existing with the chelating agent and a precipitator so as to form an atomic-scale uniform mixture of nickel hydroxide, cobalt hydroxide, aluminum hydroxide and magnesium hydroxide for precipitation, and then the atomic-scale uniform mixture is dried at a low temperature, and reconstructed and curved at a high temperature to form the magnesium nickel cobalt aluminum oxide. The molecular formula of the magnesium nickel cobalt aluminum oxide is Co<X>Mb<Y>AL<Z>Mg<H>O<X+y+z+H), wherein X is more than or equal to 7, Y is more than 0 and less than or equal to 1, Z is more than 0 and less than or equal to 1, H is more than or equal to 0.6, and X, Y, Z and H are mole number of corresponding elements.
Description
Technical field
The present invention relates to lithium-ion-power cell technical field, i.e. the preparation method and products thereof of wherein a kind of lithium dynamical battery nickel cobalt magnalium oxide.
Background technology
Along with market is to the active demand of individual character energy storage material, people more and more pay attention to the exploitation of the New Technologies of clean energy resource and energy storage material.Lithium-ion-power cell has high-energy-density, high security, the superperformance such as renewable because of it, arouses great concern.The development of special auto industry in global general population is popularized, in order to avoid the tail gas of gasoline car generation is on the impact of air, for the wide prospect that the development of electric automobile provides, thus great demand will be brought for the demand of its power lithium-ion battery positive electrode used and presoma thereof.
Current driving force lithium ion battery presoma mainly contains nickelous-nickelic oxide, cobalt sesquioxide, di iron, nickel oxide nickel, hydroxyl nickel nickel aluminium, carbonyl nickel cobalt magnalium etc., its process route prepared, according to preparation form be divided into wet method, dry method or the two go here and there and have concurrently.Chemical precipitation method is had according to the chemism of preparation, electrochemical process, oxidation-reduction method, metathesis reaction and this several mechanism comprehensive etc., the agitating mode of main reaction process has gas sparging method, advance paddling process, external force damped method etc. one or several have concurrently, the auxiliary agent of preparation process has amino-compound, one or more simultaneously dual-purposes such as ammonium salt, show according to related data, there are the following problems in the application of lithium ion power battery cathode material presoma nickel cobalt magnalium Preparation method for these technology: (1) obtained material repeatedly changes because of the dislocation of transition metal nickel ion and lithium ion and aluminum oxide crystal structure in charge and discharge process between layer structure and spinel structure, thus the expansion repeatedly causing polar body long-pending and contraction, cycle performance of battery is caused to degenerate.And LiMnO
2also exist compared with the problems of dissolution under elevated operating temperature, therefore cause in charge and discharge process, crystal structure is unstable, lattice is easily out of shape, so that other atom, electronics, ion insertion and extraction are difficult or uneven, anti-over-charging discharge performance is poor, and the chemical property of material is unstable, useful life is short, poor stability; (2) preparation process produces environmentally harmful ammonia (NH
3), ammonia nitriding compound (NH
+) etc.; (3) production cost is large and energy consumption is high.
Therefore, need now to develop a kind of cleaner production, easy and simple to handle prepare the preparation method of lithium-ion-power cell nickel cobalt magnalium oxide and the product of preparation.
Summary of the invention
The object of the invention is to, provide the preparation method of a kind of cleaner production, the lithium-ion-power cell nickel cobalt magnalium oxide that easy and simple to handle, controllability is high.
In order to solve the problems of the technologies described above, technical scheme of the present invention is: the preparation method of this lithium-ion-power cell nickel cobalt magnalium oxide, and adopt coprecipitation preparation, concrete steps are as follows:
(1) preparation feedback solution: get a certain proportion of nickel salt, cobalt salt, aluminate and magnesium salts water-soluble, forms the mixed aqueous solution of nickel salt, cobalt salt, aluminate and magnesium salts; In described mixed aqueous solution, add chelating agent mix and stir and make it mix, obtain the reaction solution with complex compound;
(2) precipitation reaction: the reaction solution with complex compound obtained in step (1) and precipitation reagent are added simultaneously respectively and carries out precipitation reaction without in magnetic response container, co-precipitation equably, form slurry;
(3) removal of impurities process: the slurry obtained in step (2) is repeatedly embathed in water, impurity such as removing inorganic salts, chelating agent etc., obtains class spherical nickel-cobalt aluminum-magnesium hydroxide matrix;
(4) dry process: the class spherical nickel-cobalt aluminum-magnesium hydroxide matrix that obtains in step (3) is put into drying box and carry out drying process;
(5) reconstruct solidification: the dried class spherical nickel-cobalt aluminum-magnesium hydroxide matrix obtained in step (4) is carried out qualitative and reconstruct solidification process, thus obtain lithium-ion-power cell nickel cobalt magnalium oxide.
Adopt technique scheme, the nickel salt of certain molar concentration, cobalt salt, magnesium salts and aluminate proportioning according to a certain percentage, under the conditions such as uniform temperature, flow, pH value, mixing speed and under the system of mixture having chelating agent, without in magnetic response container, chemical precipitation reaction is carried out with precipitation reagent, thus form the atom level homogeneous mixture of nickel hydroxide, cobalt hydroxide, magnesium hydroxide and aluminium hydroxide and precipitate, then low temperature dewatering is passed through, high-temperature reconstruction solidifies, define nickel cobalt magnalium oxide, molecular formula is Co
xmg
yaL
zni
ho
f, wherein: 2X+2Y+3Z+2H=2F, and X>=7,0 < Y≤1,0 < Z≤1, H>=0.6, X, Y, Z, H are the molal quantity of corresponding element; Complex compound is defined by chelating agent and nickel ion, aluminate ion, magnesium ion and cobalt ions when wherein first preparing reaction solution, there is certain stability, and control settling velocity like this, prevent the loose condition (of surface) of deposit seed, thus improve apparent density and the tap density of final prepared lithium-ion-power cell nickel cobalt magnalium oxide; Obtained lithium-ion-power cell nickel cobalt magnalium oxide due to each Elemental redistribution of nickel cobalt magnalium even, the effective active matter concentration of material is high, and the electrical property of the lithium battery anode made by it is excellent, and discharge platform is not easy decay, resistance to large current density, long service life; In addition introduce high price aluminium element by homogeneous phase and solve the problem that material raises because of cycle charge discharge process middle impedance, improve the active concentration of transition metal atoms in material, and aluminium atom instead of section transitions metallic atom defines solid solution to raise charging/discharging voltage platform and thermal stability, thus improve useful life and the charge/discharge capacity of material; Introduce magnesium elements by homogeneous phase to solve because of nickel ion (Ni simultaneously
2+) radius and lithium ion (Li
+) radius close to and cause the deintercalation efficiency of inconsistent phenomenon and lithium ion, magnesium atom instead of the transition metal atoms of part simultaneously, stop or eliminate the dislocation of lithium ion and transition metal ions, add the tap density of material, corresponding capacity, cycle performance and the thermal stability at high oxidation state that improve material.
Further improvement is, before described step (2) carries out precipitation reaction, the reaction solution having a complex compound by described and precipitation reagent are put into respectively and carried out purification process without the box drainer of magnetic; The time of described purification process is 2 ~ 10h.The Main Function of purification process is the chemical property being conducive to the stable of subsequent reactions and improving subsequent product; Purification process overlong time or be too shortly all unfavorable for follow-up precipitation reaction, through experimental results demonstrate, this processing time is the most favourable to follow-up precipitation reaction.
Further improvement is, the total concentration of nickel ion, cobalt ions, magnesium ion and aluminate ion in described step (1) preparation feedback solution is 50 ~ 120g/l, and described nickel salt, cobalt salt, magnesium salts and aluminate are 1000:1 ~ 18 with the ratio of the total weight of described chelating agent.
Further improvement is, mixing time when nickel salt, cobalt salt, magnesium salts and aluminate mix with described chelating agent described in described step (1) is 1 ~ 3h.In order to make chelating agent better and nickel ion, aluminium ion, cobalt ions form complex state, usually stir 1 ~ 3h by after the aqueous solution of chelating agent and nickel salt, cobalt salt, aluminate, guarantee that the nickel salt in solution, cobalt salt, aluminate fully contact with chelating agent.
Further improvement is, the described chelating agent in described step (1) is citric acid C
6h
8o
7or/and acrylic acid C
3h
4o
2; Described nickel salt is one or more mixing of nickel chloride, nickel nitrate, nickelous sulfate; Described cobalt salt is one or more mixing of cobalt chloride, cobalt nitrate, cobaltous sulfate; Described magnesium salts is that magnesium chloride is or/and magnesium nitrate; Described aluminate is that aluminic acid is received or/and potassium aluminate; Described precipitation reagent in described step (2) is that NaOH is or/and potassium hydroxide.All without containing amine groups in wherein adopted chelator acid citrate and acrylic acid, this avoid generation and the discharge of ammonia nitrogen in subsequent production process, protect environment and avoid the injury of the health to operator.
Further improvement is, reaction solution described in described step (2) is to being 1 ~ 3L/h without the speed of adding in magnetic response container, and described precipitation reagent is to being 0.5 ~ 1L/h without the speed of adding in magnetic response container simultaneously; And guarantee described reaction solution and described precipitation reagent described without being in high radial cutting force and axial turbulence in magnetic response container and having the multi-dimensional movement of choked flow, the rotating speed of paddle is 300 ~ 600 revs/min; Spoiler is that 1 ~ 20cm, pH keep 9 ~ 12 from the distance without magnetic response container, and reaction temperature is 85 ~ 105 DEG C, and the reaction time is 15 ~ 24h; Make nickel ion, cobalt ions, magnesium ion and aluminate ion under the effect of chelating agent, co-precipitation equably, form slurry.Should control in certain limit to without the speed of adding reaction solution and precipitation reagent in magnetic response container, the excessive velocities that precipitation reagent adds, granularity is difficult to control or easily wrap up other impurity, and speed is too small, and the sedimentation time is long, affects efficiency; The addition of precipitation reagent is in order to regulate the pH value of reaction simultaneously; In addition, without magnetic response container by paddle motion control movement locus and movement locus should be radial to carry out with axle same level, rotating speed is at 300 ~ 600 revs/min, and spoiler is from chamber wall 1 ~ 20 centimetre.
Further improvement is, the temperature of the water in described step (3) removal of impurities process is 85 ~ 95 DEG C.The main effect of removal of impurities process is conducive to removing the impurity such as the sodium base organic substance that generates in course of reaction; The temperature of the water therefore in removal of impurities process is determined by the kind of impurities, and some impurity that all may cause too high or too low for temperature of the water in removal of impurities process cannot be removed.
Further improvement is, in described step (4), described class spherical nickel-cobalt aluminum-magnesium hydroxide matrix is put into tray dryer machine and carry out drying process, temperature is set to 110 ~ 130 DEG C, pressure is 0 ~ 0.02Mpa, dry under the air atmosphere condition of oxygen volumn concentration 15 ~ 20%, drying time is 1.5 ~ 3h.
Further improvement is, in described step (5), described class spherical nickel-cobalt aluminum-magnesium hydroxide matrix is put into calciner and be reconstructed solidification process, temperature is set to 350 ~ 480 DEG C, pressure is 0 ~ 0.01Mpa, be reconstructed solidification in the air atmosphere of oxygen volumn concentration 15 ~ 20%, the reaction time is 3 ~ 9h.
Another technical problem that the present invention also will solve is, there is provided a kind of nickel cobalt magnalium oxide active content of material high, lattice, structure cell are regular, spherical particle is large and solid, the embedding de-freedom of other ions, electronics, migration evenly, thus improves the lithium ion power battery cathode persursor material nickel cobalt magnalium oxide of the chemical property such as capacity, platform decay of the extreme environments such as the high temperature resistant low temperature of corresponding product, the stability of structure.
In order to solve the problems of the technologies described above, technical scheme of the present invention is: the molecular formula adopting the lithium-ion-power cell nickel cobalt magnalium oxide prepared by preparation method of above-mentioned lithium-ion-power cell nickel cobalt magnalium oxide is Co
xmg
yaL
zni
ho
f, wherein: 2X+2Y+3Z+2H=2F, and X>=7,0 < Y≤1,0 < Z≤1, H>=0.6, X, Y, Z, H are the molal quantity of corresponding element.
Adopt technique scheme, the lithium-ion-power cell of the acquisition average grain diameter 18 ~ 22 μm of nickel cobalt magnalium oxide, tap density 2.5 ~ 3.0g/cm
3; The mol ratio of nickel, cobalt, aluminium, magnesium is 7 ~ 9:0.6 ~ 1.2:0.5 ~ 1:0.1 ~ 1.
Compared with prior art, the invention has the beneficial effects as follows: preparation method is simple, preparation process does not produce environmentally harmful containing ammonia nitrogen substances, and homogeneous phase introducing high price aluminium element solves the problem that material raises because of cycle charge discharge process middle impedance, improve the active concentration of transition metal atoms in material, and aluminium atom instead of section transitions metallic atom defines solid solution to raise charging/discharging voltage platform and thermal stability, thus improve useful life and the charge/discharge capacity of material; Introduce magnesium elements by homogeneous phase to solve because of nickel ion (Ni simultaneously
2+) radius and lithium ion (Li
+) radius close to and cause the deintercalation efficiency of inconsistent phenomenon and lithium ion, magnesium atom instead of the transition metal atoms of part simultaneously, stop or eliminate the dislocation of lithium ion and transition metal ions, add the tap density of material, corresponding capacity, cycle performance and the thermal stability at high oxidation state that improve material; The lithium-ion-power cell nickel cobalt magnalium oxide obtained be colorless and odorless citric acid or with acrylic acid mixture system in synthesize, be process for cleanly preparing, and each Elemental redistribution of nickel cobalt magnalium is even, the COD process of wastewater treatment process is simply; And without follow-up mixed processes, energy consumption is low; In the nickel cobalt magnalium oxide prepared, activity substance content is high, lattice, structure cell are regular, spherical particle is large and solid, the embedding de-freedom of other ions, electronics, migration evenly, thus improves the chemical property such as capacity, platform decay of the extreme environments such as the high temperature resistant low temperature of corresponding product, the stability of structure.
Accompanying drawing explanation
Fig. 1 is the stereoscan photograph of embodiment one;
Fig. 2 is the magnified sweep electromicroscopic photograph of embodiment one;
Fig. 3 is the stereoscan photograph of existing nickel cobalt manganese hydroxide;
Fig. 4 is the stereoscan photograph that magnesium types nickel cobalt manganese hydroxide mixed by existing machinery;
Fig. 5 is the grain size distribution of embodiment one;
Fig. 6 is the grain size distribution of existing nickel cobalt manganese hydroxide;
Fig. 7 is the grain size distribution that magnesium types nickel cobalt manganese hydroxide mixed by existing machinery.
Embodiment
Embodiment one: this lithium-ion-power cell preparation method of nickel cobalt magnalium oxide, adopt coprecipitation preparation, concrete steps are as follows:
(1) preparation feedback solution: add nickel chloride 1037.5g respectively in 3500ml water, cobalt chloride 130g, 64g and magnesium chloride 19g received by aluminic acid, fully mixes, and adds 1.5g acrylic acid C
3h
4o
2chelating agent carries out stirring 2.5h and mixes, the obtained reaction solution with complex compound;
(2) purification process: the reaction solution and precipitation reagent 40% potassium hydroxide solution with complex compound are put into respectively and carry out purification process without the box ultrafiltration container of magnetic, the processing time is 4h, obtains the reaction solution after purifying and the precipitation reagent after purifying respectively;
(3) precipitation reaction: by reaction solution with the speed of 1.7L/h, precipitation reagent adds without in magnetic response still with the Rate Dispersion of 0.7L/h simultaneously, in the liquid phase environment having High Linear cutting force axial flow, radial turbulent flow concurrently, control reaction temperature is 98 DEG C, pH value 10 ~ 10.5, the rotating speed of paddle is 400 revs/min; Spoiler is 8cm from the distance without magnetic response container, and the reaction time is 16h; Make nickel, cobalt, magnesium ion and aluminate ion by the affinity co-precipitation of hydroxyl bond, affinity co-precipitation reconstructs modification in the mode of laminar flow later in its natural state, obtain average grain diameter be 21 μm spherical nickel cobalt magnalium quaternary hydroxides, inorganic salts, chelating agent the slurry of mixture;
(4) removal of impurities process: this slurry removes inorganic salts, chelating agent in 90 DEG C of aqueous systems, obtained spherical nickel cobalt aluminum-magnesium hydroxide matrix;
(5) dry process: this spherical nickel cobalt aluminum-magnesium hydroxide matrix is put into tray dryer machine, 120 ± 5 DEG C, oxygen content is in the air of 18 ± 1%, 0.01Mpa pressure (gauge pressure), the processing time is that 2h carries out dry process of anhydrating;
(6) reconstruct solidification: the spherical nickel cobalt aluminum-magnesium hydroxide matrix after drying process is moved into calciner, set temperature is 450 ± 5 DEG C, oxygen content is in the air of 18 ± 1%, be reconstructed solidification under the condition of 0.01Mpa pressure (gauge pressure), curing time is 5h, obtains tap density 2.8g/cm
3, average grain diameter 20.49 μm power lithium-ion battery positive electrode material precursor nickel cobalt magnalium oxide (nickel, cobalt, aluminium, magnesium mol ratio are 8:1:0.8:0.2); Its sample through ICP testing result as following table 1:
Table 1: the test result of the mass spectrum (ICP) of the cobalt magnesium Mn oxide obtained by embodiment 1
| Project | Unit | Measured data |
| Nickel (Ni) | wt％ | 62.36 |
| Cobalt (Co) | wt％ | 8.45 |
| Aluminium (Al) | wt％ | 1.40 |
| Magnesium (Mg) | wt％ | 0.62 |
| Iron (Fe) | wt％ | 0.0015 |
| Copper (Cu) | wt％ | No |
| Chromium (Cr) | wt％ | No |
| Sodium (Na) | wt％ | 0.0250 |
| Plumbous (Pb) | wt％ | 0.0028 |
| Magnetic foreign body | BBP | 36 |
Its main performance index test result compares, as following table 2 with existing same type of material performance:
Table 2: the cobalt magnesium Mn oxide obtained by embodiment 1 and the Performance comparision of existing same type of material
Embodiment two: this lithium-ion-power cell preparation method of nickel cobalt magnalium oxide, adopt coprecipitation preparation, concrete steps are as follows:
(1) preparation feedback solution: add nickel chloride 972.7g respectively in 3000ml water, cobalt chloride 130g, 80g and magnesium chloride 47.6g received by aluminic acid, fully mixes, and adds the citric acid C that 3.2g weight ratio is 2:1
6h
8o
7with acrylic acid C
3h
4o
2the chelating agent of mixture carries out stirring 2.5h and mixes, the obtained reaction solution with complex compound;
(2) purification process: the reaction solution and precipitation reagent 40% sodium hydroxide solution with complex compound are put into respectively and carry out purification process without the box ultrafiltration container of magnetic, the processing time is 2h, obtains the reaction solution after purifying and the precipitation reagent after purifying respectively;
(3) precipitation reaction: by reaction solution with the speed of 1.8L/h, precipitation reagent adds without in magnetic response still with the Rate Dispersion of 0.82L/h simultaneously, in the liquid phase environment having High Linear cutting force axial flow, radial turbulent flow concurrently, control reaction temperature is 95 DEG C, pH value 9.6 ~ 10.1, the rotating speed of paddle is 350 revs/min; Spoiler is 8cm from the distance without magnetic response container, and the reaction time is 20h; Make nickel, cobalt, magnesium ion and aluminate ion by the affinity co-precipitation of hydroxyl bond, affinity co-precipitation reconstructs modification in the mode of laminar flow later in its natural state, obtain average grain diameter be 20.5 μm spherical nickel cobalt magnalium quaternary hydroxides, inorganic salts, chelating agent the slurry of mixture;
(4) removal of impurities process: this slurry removes inorganic salts, chelating agent in 95 DEG C of aqueous systems, obtained spherical nickel cobalt aluminum-magnesium hydroxide matrix;
(5) dry process: this spherical nickel cobalt aluminum-magnesium hydroxide matrix is put into tray dryer machine, 120 ± 5 DEG C, oxygen content is in the air of 18 ± 1%, 0.01Mpa pressure (gauge pressure), the processing time is that 2h carries out dry process of anhydrating;
(6) reconstruct solidification: the spherical nickel cobalt aluminum-magnesium hydroxide matrix after drying process is moved into calciner, set temperature is 410 ± 5 DEG C, oxygen content is in the air of 18 ± 1%, be reconstructed solidification under the condition of 0.01Mpa pressure (gauge pressure), curing time is 7h, obtains tap density 2.6g/cm
3, average grain diameter 20 μm power lithium-ion battery positive electrode material precursor nickel cobalt magnalium oxide (nickel, cobalt, aluminium, magnesium mol ratio are 7.5:1:1:0.5).
Embodiment three: this lithium-ion-power cell preparation method of nickel cobalt magnalium oxide, adopt coprecipitation preparation, concrete steps are as follows:
(1) preparation feedback solution: add nickel chloride 1011.6g respectively in 3900ml water, cobalt chloride 130g, 80g and magnesium chloride 19g received by aluminic acid, fully mixes, and adds 3.2g acrylic acid C
3h
4o
2chelating agent carries out stirring 2.5h and mixes, the obtained reaction solution with complex compound;
(2) purification process: the reaction solution and precipitation reagent 40% sodium hydroxide solution with complex compound are put into respectively and carry out purification process without the box ultrafiltration container of magnetic, the processing time is 3h, obtains the reaction solution after purifying and the precipitation reagent after purifying respectively;
(3) precipitation reaction: by reaction solution with the speed of 1.5L/h, precipitation reagent adds without in magnetic response still with the Rate Dispersion of 0.6L/h simultaneously, in the liquid phase environment having High Linear cutting force axial flow, radial turbulent flow concurrently, control reaction temperature is 98 DEG C, pH value 10 ~ 10.5, the rotating speed of paddle is 450 revs/min; Spoiler is 5cm from the distance without magnetic response container, and the reaction time is 20h; Make nickel, cobalt, magnesium ion and aluminate ion by the affinity co-precipitation of hydroxyl bond, affinity co-precipitation reconstructs modification in the mode of laminar flow later in its natural state, obtain average grain diameter be 19.5 μm spherical nickel cobalt magnalium quaternary hydroxides, inorganic salts, chelating agent the slurry of mixture;
(4) removal of impurities process: this slurry removes inorganic salts, chelating agent in 85 DEG C of aqueous systems, obtained spherical nickel cobalt aluminum-magnesium hydroxide matrix;
(5) dry process: this spherical nickel cobalt aluminum-magnesium hydroxide matrix is put into tray dryer machine, 120 ± 5 DEG C, oxygen content is in the air of 18 ± 1%, 0.01Mpa pressure (gauge pressure), the processing time is that 2h carries out dry process of anhydrating;
(6) reconstruct solidification: the spherical nickel cobalt aluminum-magnesium hydroxide matrix after drying process is moved into calciner, set temperature is 380 ± 5 DEG C, oxygen content is in the air of 18 ± 1%, be reconstructed solidification under the condition of 0.01Mpa pressure (gauge pressure), curing time is 7h, obtains tap density 2.7g/cm
3, average grain diameter 19 μm power lithium-ion battery positive electrode material precursor nickel cobalt magnalium oxide (nickel, cobalt, aluminium, magnesium mol ratio are 7.8:1:1:0.2).
Embodiment four: this lithium-ion-power cell preparation method of nickel cobalt magnalium oxide, adopt coprecipitation preparation, concrete steps are as follows:
(1) preparation feedback solution: add nickel chloride 933.8g respectively in 4000ml water, cobalt chloride 130g, potassium aluminate 80g and magnesium chloride 76.2g, fully mix, and add the citric acid C that 3.5g weight ratio is 2:1
6h
8o
7with acrylic acid C
3h
4o
2the chelating agent of mixture carries out stirring 3h and mixes, the obtained reaction solution with complex compound;
(2) purification process: the reaction solution and precipitation reagent 30% potassium hydroxide solution with complex compound are put into respectively and carry out purification process without the box ultrafiltration container of magnetic, the processing time is 3h, obtains the reaction solution after purifying and the precipitation reagent after purifying respectively;
(3) precipitation reaction: by reaction solution with the speed of 1.5L/h, precipitation reagent adds without in magnetic response still with the Rate Dispersion of 0.7L/h simultaneously, in the liquid phase environment having High Linear cutting force axial flow, radial turbulent flow concurrently, control reaction temperature is 95 DEG C, pH value 9.8 ~ 10.3, the rotating speed of paddle is 350 revs/min; Spoiler is 10cm from the distance without magnetic response container, and the reaction time is 20h; Make nickel, cobalt, magnesium ion and aluminate ion by the affinity co-precipitation of hydroxyl bond, affinity co-precipitation reconstructs modification in the mode of laminar flow later in its natural state, obtain average grain diameter be 20.5 μm spherical nickel cobalt magnalium quaternary hydroxides, inorganic salts, chelating agent the slurry of mixture;
(4) removal of impurities process: this slurry removes inorganic salts, chelating agent in 95 DEG C of aqueous systems, obtained spherical nickel cobalt aluminum-magnesium hydroxide matrix;
(5) dry process: this spherical nickel cobalt aluminum-magnesium hydroxide matrix is put into tray dryer machine, 120 ± 5 DEG C, oxygen content is in the air of 18 ± 1%, 0.01Mpa pressure (gauge pressure), the processing time is that 2h carries out dry process of anhydrating;
(6) reconstruct solidification: the spherical nickel cobalt aluminium hydroxide matrix after drying process is moved into calciner, set temperature is 400 ± 5 DEG C, oxygen content is in the air of 18 ± 1%, be reconstructed solidification under the condition of 0.01Mpa pressure (gauge pressure), curing time is 6.5h, obtains tap density 2.7g/cm
3, average grain diameter 20 μm power lithium-ion battery positive electrode material precursor nickel cobalt magnalium oxide (nickel, cobalt, aluminium, magnesium mol ratio are 7.2:1:1:0.8).
Embodiment five: this lithium-ion-power cell preparation method of nickel cobalt magnalium oxide, adopt coprecipitation preparation, concrete steps are as follows:
(1) preparation feedback solution: add nickel chloride 907.9g respectively in 3200ml water, cobalt chloride 130g, 80g and magnesium chloride 95.3g received by aluminic acid, fully mixes, and adds 3.8g citric acid C
6h
8o
7chelating agent carries out stirring 2h and mixes, the obtained reaction solution with complex compound;
(2) purification process: the reaction solution and precipitation reagent 30% sodium hydroxide solution with complex compound are put into respectively and carry out purification process without the box ultrafiltration container of magnetic, the processing time is 4h, obtains the reaction solution after purifying and the precipitation reagent after purifying respectively;
(3) precipitation reaction: by reaction solution with the speed of 1.6L/h, precipitation reagent adds without in magnetic response still with the Rate Dispersion of 0.8L/h simultaneously, in the liquid phase environment having High Linear cutting force axial flow, radial turbulent flow concurrently, control reaction temperature is 90 DEG C, pH value 9.8 ~ 10.2, the rotating speed of paddle is 400 revs/min; Spoiler is 10cm from the distance without magnetic response container, and the reaction time is 18h; Make nickel, cobalt, magnesium ion and aluminate ion by the affinity co-precipitation of hydroxyl bond, affinity co-precipitation reconstructs modification in the mode of laminar flow later in its natural state, obtain average grain diameter be 19 μm spherical nickel cobalt magnalium quaternary hydroxides, inorganic salts, chelating agent the slurry of mixture;
(4) removal of impurities process: this slurry removes inorganic salts, chelating agent in 90 DEG C of aqueous systems, obtained spherical nickel cobalt aluminum-magnesium hydroxide matrix;
(5) dry process: this spherical nickel cobalt aluminum-magnesium hydroxide matrix is put into tray dryer machine, 120 ± 5 DEG C, oxygen content is in the air of 18 ± 1%, 0.01Mpa pressure (gauge pressure), the processing time is that 2h carries out dry process of anhydrating;
(6) reconstruct solidification: the spherical nickel cobalt aluminum-magnesium hydroxide matrix after drying process is moved into calciner, set temperature is 400 ± 5 DEG C, oxygen content is in the air of 18 ± 1%, be reconstructed solidification under the condition of 0.01Mpa pressure (gauge pressure), curing time is 7.5h, obtains tap density 2.8g/cm
3, average grain diameter 18.5 μm power lithium-ion battery positive electrode material precursor nickel cobalt magnalium oxide (nickel, cobalt, aluminium, magnesium mol ratio are 7:1:1:1).
Embodiment six: this lithium-ion-power cell preparation method of nickel cobalt magnalium oxide, adopt coprecipitation preparation, concrete steps are as follows:
(1) preparation feedback solution: add nickel chloride 1037.5g respectively in 4500ml water, cobalt chloride 104g, 80g and magnesium chloride 19g received by aluminic acid, fully mixes, and adds 3.6g acrylic acid C
3h
4o
2chelating agent carries out stirring 3.0h and mixes, the obtained reaction solution with complex compound;
(2) purification process: the reaction solution and precipitation reagent 40% sodium hydroxide solution with complex compound are put into respectively and carry out purification process without the box ultrafiltration container of magnetic, the processing time is 2h, obtains the reaction solution after purifying and the precipitation reagent after purifying respectively;
(3) precipitation reaction: by reaction solution with the speed of 1.8L/h, precipitation reagent adds without in magnetic response still with the Rate Dispersion of 0.8L/h simultaneously, in the liquid phase environment having High Linear cutting force axial flow, radial turbulent flow concurrently, control reaction temperature is 95 DEG C, pH value 9.8 ~ 10.3, the rotating speed of paddle is 450 revs/min; Spoiler is 5cm from the distance without magnetic response container, and the reaction time is 20h; Make nickel, cobalt, magnesium ion and aluminate ion by the affinity co-precipitation of hydroxyl bond, affinity co-precipitation reconstructs modification in the mode of laminar flow later in its natural state, obtain average grain diameter be 20 μm spherical nickel cobalt magnalium quaternary hydroxides, inorganic salts, chelating agent the slurry of mixture;
(4) removal of impurities process: this slurry removes inorganic salts, chelating agent in 95 DEG C of aqueous systems, obtained spherical nickel cobalt aluminum-magnesium hydroxide matrix;
(5) dry process: this spherical nickel cobalt aluminum-magnesium hydroxide matrix is put into tray dryer machine, 120 ± 5 DEG C, oxygen content is in the air of 18 ± 1%, 0.01Mpa pressure (gauge pressure), the processing time is that 2h carries out dry process of anhydrating;
(6) reconstruct solidification: the spherical nickel cobalt aluminum-magnesium hydroxide matrix after drying process is moved into calciner, set temperature is 400 ± 5 DEG C, oxygen content is in the air of 18 ± 1%, be reconstructed solidification under the condition of 0.01Mpa pressure (gauge pressure), curing time is 6h, obtains tap density 2.7g/cm
3, average grain diameter 19.5 μm power lithium-ion battery positive electrode material precursor nickel cobalt magnalium oxide (nickel, cobalt, aluminium, magnesium mol ratio are 8:0.8:1:0.2).
Embodiment seven: this lithium-ion-power cell preparation method of nickel cobalt magnalium oxide, adopt coprecipitation preparation, concrete steps are as follows:
(1) preparation feedback solution: add nickel nitrate 1621.5g respectively in 4300ml water, cobalt nitrate 121.8g, potassium aluminate 78.4g and magnesium nitrate 101g, fully mix, and add the citric acid C that 4g weight ratio is 2:1
6h
8o
7with acrylic acid C
3h
4o
2the chelating agent of mixture carries out stirring 3h and mixes, the obtained reaction solution with complex compound;
(2) purification process: the reaction solution and precipitation reagent 40% sodium hydroxide solution with complex compound are put into respectively and carry out purification process without the box ultrafiltration container of magnetic, the processing time is 3h, obtains the reaction solution after purifying and the precipitation reagent after purifying respectively;
(3) precipitation reaction: by reaction solution with the speed of 1.9L/h, precipitation reagent adds without in magnetic response still with the Rate Dispersion of 0.85L/h simultaneously, in the liquid phase environment having High Linear cutting force axial flow, radial turbulent flow concurrently, control reaction temperature is 95 DEG C, pH value 9.8 ~ 10.3, the rotating speed of paddle is 400 revs/min; Spoiler is 8cm from the distance without magnetic response container, and the reaction time is 24h; Make nickel, cobalt, magnesium ion and aluminate ion by the affinity co-precipitation of hydroxyl bond, affinity co-precipitation reconstructs modification in the mode of laminar flow later in its natural state, obtain average grain diameter be 20.4 μm spherical nickel cobalt magnalium quaternary hydroxides, inorganic salts, chelating agent the slurry of mixture;
(4) removal of impurities process: this slurry removes inorganic salts, chelating agent in 85 DEG C of aqueous systems, obtained spherical nickel cobalt aluminum-magnesium hydroxide matrix;
(5) dry process: this spherical nickel cobalt aluminum-magnesium hydroxide matrix is put into tray dryer machine, 120 ± 5 DEG C, oxygen content is in the air of 18 ± 1%, 0.01Mpa pressure (gauge pressure), the processing time is that 2h carries out dry process of anhydrating;
(6) reconstruct solidification: the spherical nickel cobalt aluminum-magnesium hydroxide matrix after drying process is moved into calciner, set temperature is 420 ± 5 DEG C, oxygen content is in the air of 18 ± 1%, be reconstructed solidification under the condition of 0.01Mpa pressure (gauge pressure), curing time is 5.8h, obtains tap density 2.8g/cm
3, average grain diameter 20 μm power lithium-ion battery positive electrode material precursor nickel cobalt magnalium oxide (nickel, cobalt, aluminium, magnesium mol ratio are 8:0.6:0.8:0.6).
Embodiment eight: this lithium-ion-power cell preparation method of nickel cobalt magnalium oxide, adopt coprecipitation preparation, concrete steps are as follows:
(1) preparation feedback solution: add nickel nitrate 1581g respectively in 4500ml water, cobalt nitrate 203g, potassium aluminate 78.4g and magnesium nitrate 67.3g, fully mix, and add the citric acid C that 3.6g weight ratio is 2:1
6h
8o
7with acrylic acid C
3h
4o
2the chelating agent of mixture carries out stirring 2.5h and mixes, the obtained reaction solution with complex compound;
(2) purification process: the reaction solution and precipitation reagent 30% potassium hydroxide solution with complex compound are put into respectively and carry out purification process without the box ultrafiltration container of magnetic, the processing time is 2h, obtains the reaction solution after purifying and the precipitation reagent after purifying respectively;
(3) precipitation reaction: by reaction solution with the speed of 1.8L/h, precipitation reagent adds without in magnetic response still with the Rate Dispersion of 0.8L/h simultaneously, in the liquid phase environment having High Linear cutting force axial flow, radial turbulent flow concurrently, control reaction temperature is 96 DEG C, pH value 9.8 ~ 10.2, the rotating speed of paddle is 350 revs/min; Spoiler is 10cm from the distance without magnetic response container, and the reaction time is 16h; Make nickel, cobalt, magnesium ion and aluminate ion by the affinity co-precipitation of hydroxyl bond, affinity co-precipitation reconstructs modification in the mode of laminar flow later in its natural state, obtain average grain diameter be 19.5 μm spherical nickel cobalt magnalium quaternary hydroxides, inorganic salts, chelating agent the slurry of mixture;
(4) removal of impurities process: this slurry removes inorganic salts, chelating agent in 90 DEG C of aqueous systems, obtained spherical nickel cobalt aluminum-magnesium hydroxide matrix;
(5) dry process: this spherical nickel cobalt aluminum-magnesium hydroxide matrix is put into tray dryer machine, 120 ± 5 DEG C, oxygen content is in the air of 18 ± 1%, 0.01Mpa pressure (gauge pressure), the processing time is that 2h carries out dry process of anhydrating;
(6) reconstruct solidification: the spherical nickel cobalt aluminum-magnesium hydroxide matrix after drying process is moved into calciner, set temperature is 420 ± 5 DEG C, oxygen content is in the air of 18 ± 1%, be reconstructed solidification under the condition of 0.01Mpa pressure (gauge pressure), curing time is 6.5h, obtains tap density 2.9g/cm
3, average grain diameter 19.2 μm power lithium-ion battery positive electrode material precursor nickel cobalt magnalium oxide (nickel, cobalt, aluminium, magnesium mol ratio are 7.8:1:0.8:0.4).
Embodiment nine: this lithium-ion-power cell preparation method of nickel cobalt magnalium oxide, adopt coprecipitation preparation, concrete steps are as follows:
(1) preparation feedback solution: add nickel nitrate 1520g respectively in 4000ml water, cobalt nitrate 162.3g, potassium aluminate 98g and magnesium nitrate 117.8g, fully mix, and add the citric acid C that 3.5g weight ratio is 2:1
6h
8o
7with acrylic acid C
3h
4o
2the chelating agent of mixture carries out stirring 2.5h and mixes, the obtained reaction solution with complex compound;
(2) purification process: the reaction solution and precipitation reagent 30% potassium hydroxide solution with complex compound are put into respectively and carry out purification process without the box ultrafiltration container of magnetic, the processing time is 3h, obtains the reaction solution after purifying and the precipitation reagent after purifying respectively;
(3) precipitation reaction: by reaction solution with the speed of 1.8L/h, precipitation reagent adds without in magnetic response still with the Rate Dispersion of 0.8L/h simultaneously, in the liquid phase environment having High Linear cutting force axial flow, radial turbulent flow concurrently, control reaction temperature is 98 DEG C, pH value 10.0 ~ 10.5, the rotating speed of paddle is 400 revs/min; Spoiler is 5cm from the distance without magnetic response container, and the reaction time is 20h; Make nickel, cobalt, magnesium ion and aluminate ion by the affinity co-precipitation of hydroxyl bond, affinity co-precipitation reconstructs modification in the mode of laminar flow later in its natural state, obtain average grain diameter be 20 μm spherical nickel cobalt magnalium quaternary hydroxides, inorganic salts, chelating agent the slurry of mixture;
(4) removal of impurities process: this slurry removes inorganic salts, chelating agent in 95 DEG C of aqueous systems, obtained spherical nickel cobalt aluminum-magnesium hydroxide matrix;
(5) dry process: this spherical nickel cobalt aluminum-magnesium hydroxide matrix is put into tray dryer machine, 120 ± 5 DEG C, oxygen content is in the air of 18 ± 1%, 0.01Mpa pressure (gauge pressure), the processing time is that 2h carries out dry process of anhydrating;
(6) reconstruct solidification: the spherical nickel cobalt aluminum-magnesium hydroxide matrix after drying process is moved into calciner, set temperature is 400 ± 5 DEG C, oxygen content is in the air of 18 ± 1%, be reconstructed solidification under the condition of 0.01Mpa pressure (gauge pressure), curing time is 6.5h, obtains tap density 2.8g/cm
3, average grain diameter 19.6 μm power lithium-ion battery positive electrode material precursor nickel cobalt magnalium oxide (nickel, cobalt, aluminium, magnesium mol ratio are 7.5:0.8:1:0.7).
Embodiment ten: this lithium-ion-power cell preparation method of nickel cobalt magnalium oxide, adopt coprecipitation preparation, concrete steps are as follows:
(1) preparation feedback solution: add nickel nitrate 1581g respectively in 4500ml water, cobalt nitrate 223.2g, potassium aluminate 98g and magnesium nitrate 16.8g, fully mix, and add the citric acid C that 4.0g weight ratio is 2:1
6h
8o
7with acrylic acid C
3h
4o
2the chelating agent of mixture carries out stirring 3h and mixes, the obtained reaction solution with complex compound;
(2) purification process: the reaction solution and precipitation reagent 30% potassium hydroxide solution with complex compound are put into respectively and carry out purification process without the box ultrafiltration container of magnetic, the processing time is 4h, obtains the reaction solution after purifying and the precipitation reagent after purifying respectively;
(3) precipitation reaction: by reaction solution with the speed of 2.0L/h, precipitation reagent adds without in magnetic response still with the Rate Dispersion of 0.9L/h simultaneously, in the liquid phase environment having High Linear cutting force axial flow, radial turbulent flow concurrently, control reaction temperature is 95 DEG C, pH value 9.8 ~ 10.3, the rotating speed of paddle is 300 revs/min; Spoiler is 10cm from the distance without magnetic response container, and the reaction time is 20h; Make nickel, cobalt, magnesium ion and aluminate ion by the affinity co-precipitation of hydroxyl bond, affinity co-precipitation reconstructs modification in the mode of laminar flow later in its natural state, obtain average grain diameter be 21.5 μm spherical nickel cobalt magnalium quaternary hydroxides, inorganic salts, chelating agent the slurry of mixture;
(4) removal of impurities process: this slurry removes inorganic salts, chelating agent in 88 DEG C of aqueous systems, obtained spherical nickel cobalt aluminum-magnesium hydroxide matrix;
(5) dry process: this spherical nickel cobalt aluminum-magnesium hydroxide matrix is put into tray dryer machine, 120 ± 5 DEG C, oxygen content is in the air of 18 ± 1%, 0.01Mpa pressure (gauge pressure), the processing time is that 2h carries out dry process of anhydrating;
(6) reconstruct solidification: the spherical nickel cobalt aluminum-magnesium hydroxide matrix after drying process is moved into calciner, set temperature is 400 ± 5 DEG C, oxygen content is in the air of 18 ± 1%, be reconstructed solidification under the condition of 0.01Mpa pressure (gauge pressure), curing time is 6h, obtains tap density 2.75g/cm
3, average grain diameter 21 μm power lithium-ion battery positive electrode material precursor nickel cobalt magnalium oxide (nickel, cobalt, aluminium, magnesium mol ratio are 7.8:1.1:1:0.1).
More than show and describe general principle of the present invention, principal character and advantage.The technical staff of the industry should understand; the present invention is not restricted to the described embodiments; what describe in above-described embodiment and specification just illustrates principle of the present invention; without departing from the spirit and scope of the present invention; the present invention also has various changes and modifications; these changes and improvements all fall in the claimed scope of the invention, such as, change some reaction time and reaction temperature simultaneously or in proportion, change the weight etc. of raw material, also can realize identical technique effect.Application claims protection range is defined by appending claims and equivalent thereof.
Claims (10)
1. a lithium-ion-power cell preparation method for nickel cobalt magnalium oxide, is characterized in that, this lithium-ion-power cell nickel cobalt magnalium oxide adopts coprecipitation preparation, and concrete steps are as follows:
(1) preparation feedback solution: get a certain proportion of nickel salt, cobalt salt, aluminate and magnesium salts water-soluble, forms the mixed aqueous solution of nickel salt, cobalt salt, aluminate and magnesium salts; In described mixed aqueous solution, add chelating agent mix and stir and make it mix, obtain the reaction solution with complex compound;
(2) precipitation reaction: the reaction solution with complex compound obtained in step (1) and precipitation reagent are added simultaneously respectively and carries out precipitation reaction without in magnetic response container, co-precipitation equably, form slurry;
(3) removal of impurities process: the slurry obtained in step (2) is repeatedly embathed in water, impurity such as removing inorganic salts, chelating agent etc., obtains class spherical nickel-cobalt aluminum-magnesium hydroxide matrix;
(4) dry process: the class spherical nickel-cobalt aluminum-magnesium hydroxide matrix that obtains in step (3) is put into drying box and carry out drying process;
(5) reconstruct solidification: the dried class spherical nickel-cobalt aluminum-magnesium hydroxide matrix obtained in step (4) is carried out qualitative and reconstruct solidification process, thus obtain lithium-ion-power cell nickel cobalt magnalium oxide.
2. the preparation method of lithium-ion-power cell nickel cobalt magnalium oxide according to claim 1, it is characterized in that, before described step (2) carries out precipitation reaction, the reaction solution having a complex compound by described and precipitation reagent are put into respectively and are carried out purification process without the box drainer of magnetic; The time of described purification process is 2 ~ 10h.
3. the preparation method of lithium-ion-power cell nickel cobalt magnalium oxide according to claim 2, it is characterized in that, the total concentration of nickel ion, cobalt ions, magnesium ion and aluminate ion in described step (1) preparation feedback solution is 50 ~ 120g/L, and described nickel salt, cobalt salt, magnesium salts and aluminate are 1000:1 ~ 18 with the ratio of the total weight of described chelating agent.
4. the preparation method of nickel cobalt magnalium oxide of the lithium-ion-power cell according to Claims 2 or 3, it is characterized in that, mixing time when nickel salt, cobalt salt, magnesium salts and aluminate mix with described chelating agent described in described step (1) is 1 ~ 3h.
5. the preparation method of lithium-ion-power cell nickel cobalt magnalium oxide according to claim 4, it is characterized in that, the described chelating agent in described step (1) is citric acid C
6h
8o
7or/and acrylic acid C
3h
4o
2; Described nickel salt is one or more mixing of nickel chloride, nickel nitrate, nickelous sulfate; Described cobalt salt is one or more mixing of cobalt chloride, cobalt nitrate, cobaltous sulfate; Described magnesium salts is that magnesium chloride is or/and magnesium nitrate; Described aluminate is that aluminic acid is received or/and potassium aluminate; Described precipitation reagent in described step (2) is that NaOH is or/and potassium hydroxide.
6. the preparation method of lithium-ion-power cell nickel cobalt magnalium oxide according to claim 5, it is characterized in that, reaction solution described in described step (2) is to being 1 ~ 3L/h without the speed of adding in magnetic response container, and described precipitation reagent is to being 0.5 ~ 1L/h without the speed of adding in magnetic response container simultaneously; And guarantee described reaction solution and described precipitation reagent described without being in high radial cutting force and axial turbulence in magnetic response container and having the multi-dimensional movement of choked flow, the rotating speed of paddle is 300 ~ 600 revs/min; Spoiler is that 1 ~ 20cm, pH keep 9 ~ 12 from the distance without magnetic response container, and reaction temperature is 85 ~ 105 DEG C, and the reaction time is 15 ~ 24h; Make nickel ion, cobalt ions, magnesium ion and aluminate ion under the effect of chelating agent, co-precipitation equably, form slurry.
7. the preparation method of lithium-ion-power cell nickel cobalt magnalium oxide according to claim 6, it is characterized in that, the temperature of the water in described step (3) removal of impurities process is 85 ~ 95 DEG C.
8. the preparation method of lithium-ion-power cell nickel cobalt magnalium oxide according to claim 7, it is characterized in that, in described step (4), described class spherical nickel-cobalt aluminum-magnesium hydroxide matrix is put into tray dryer machine and carry out drying process, temperature is set to 110 ~ 130 DEG C, pressure is 0 ~ 0.02Mpa, dry under the air atmosphere condition of oxygen volumn concentration 15 ~ 20%, drying time is 1.5 ~ 3h.
9. the preparation method of lithium-ion-power cell nickel cobalt magnalium oxide according to claim 8, it is characterized in that, in described step (5), described class spherical nickel-cobalt aluminum-magnesium hydroxide matrix is put into calciner and be reconstructed solidification process, temperature is set to 350 ~ 480 DEG C, pressure is 0 ~ 0.01Mpa, be reconstructed solidification in the air atmosphere of oxygen volumn concentration 15 ~ 20%, the reaction time is 3 ~ 9h.
10. one kind adopts the lithium-ion-power cell nickel cobalt magnalium oxide prepared by the preparation method of the nickel cobalt magnalium oxide of the lithium-ion-power cell as described in any one of claim 1-9, it is characterized in that, the molecular formula of the lithium-ion-power cell nickel cobalt magnalium oxide of acquisition is Co
xmg
yaL
zni
ho
f, wherein: 2X+2Y+3Z+2H=2F, and X>=7,0 < Y≤1,0 < Z≤1, H>=0.6, X, Y, Z, H are the molal quantity of corresponding element.
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| CN115745011A (en) * | 2022-11-18 | 2023-03-07 | 金川集团股份有限公司 | Preparation method of aluminum-doped small-particle-size spherical cobaltosic oxide for high-voltage lithium cobaltate |
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