CN105140507A - Preparation method of Co-Mg-Mn oxide for lithium ion power battery and product - Google Patents
Preparation method of Co-Mg-Mn oxide for lithium ion power battery and product Download PDFInfo
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- CN105140507A CN105140507A CN201510398045.3A CN201510398045A CN105140507A CN 105140507 A CN105140507 A CN 105140507A CN 201510398045 A CN201510398045 A CN 201510398045A CN 105140507 A CN105140507 A CN 105140507A
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- 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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Abstract
The invention relates to a preparation method of a Co-Mg-Mn oxide for a lithium ion power battery. A co-precipitation method is adopted and the preparation method comprises the following steps of: (1) preparing a reaction solution; (2) carrying out purification treatment; (3) carrying out co-precipitation reaction; (4) removing impurities; and (5) carrying out heat stabilizing. Chemical precipitation reaction of a certain molar concentration of a cobalt salt, a magnesium salt and a manganese salt according to a certain proportion with a precipitator is carried out in a reaction kettle compatible with a radial flow and an axial flow under conditions of a certain temperature, a flow rate, a pH value, a stirring speed and the like and in a system of a mixture with the presence of a slow controlled agent to form an atomic-scale uniform mixture of cobalt hydroxide, magnesium hydroxide and manganese hydroxide for precipitation, and then low-temperature dehydration and high-temperature reconstitution are carried out to form the Co-Mg-Mn oxide, the formula of the Co-Mg-Mn oxide is Co<X>Mn<Y>Mg<Z>O4, wherein (X+Y+Z) is more than 0 but less than or equal to 3, X is more than 0, (X+Y) is more than 0 and less than 2, and Z is more than 0 but less than or equal to 0.1.
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 cobalt magnesium Mn oxide.
Background technology
Along with people, 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 cobaltosic oxide, manganese sesquioxide managnic oxide, di iron, cobalt oxide nickel, hydroxyl nickel cobalt manganese, carbonyl cobalt magnesium manganese 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 cobalt magnesium Mn oxide preparation method for these technology: (1) obtained material repeatedly changes because of the dislocation of transition metal cobalt ions and lithium ion and Mn 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 cobalt magnesium Mn 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 cobalt magnesium Mn 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 cobalt magnesium Mn oxide, and adopt coprecipitation preparation, concrete steps are as follows:
(1) prepare reaction solution: get a certain proportion of cobalt salt, magnesium salts and manganese salt water-soluble, form the mixed aqueous solution of cobalt salt, magnesium salts and manganese salt; In described mixed aqueous solution, add slow control agent mix and stir and make it mix, obtain reaction solution;
(2) purification process: the precipitation reagent needed for the reaction solution prepared in step (1) and reaction is put into carry out purified treatment without the box ultrafiltration container of magnetic respectively;
(3) coprecipitation reaction: the reaction solution in step (2) after purification process and precipitation reagent are added in reaction vessel simultaneously and carry out precipitation reaction, co-precipitation equably, forms slurry; Described reaction vessel is the reaction vessel having radial flow and axial flow concurrently;
(4) removal of impurities process: the slurry obtained in step (3) is repeatedly embathed in water, the impurity such as removing inorganic salts, slow control agent, obtain class spherical cobalt magnesium manganese hydroxide matrix;
(5) heat setting process: institute's class that obtains spherical cobalt magnesium manganese hydroxide matrix in step (4) is carried out drying and heat setting process, thus obtains lithium-ion-power cell cobalt magnesium Mn oxide.
Adopt technique scheme, the cobalt salt of certain molar concentration, magnesium salts, manganese salt 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 a slow control agent, in the reaction vessel having radial flow and axial flow concurrently, chemical precipitation reaction is carried out with precipitation reagent, thus formed cobalt hydroxide, magnesium hydroxide, manganous hydroxide atom level homogeneous mixture and precipitate, then low temperature dewatering is passed through, high-temperature reconstruction, define cobalt magnesium Mn oxide, molecular formula is Co
xmn
ymg
zo
4, wherein: 0<X+Y+Z≤3, X > 0,0<X+Y<2,0<Z≤0.1; Complex compound is defined by slow control agent and cobalt ions, manganese ion, magnesium ion 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 cobalt magnesium Mn oxide; The Main Function of purification process is the chemical property being conducive to the stable of subsequent reactions and improving subsequent product; Obtained lithium-ion-power cell cobalt magnesium Mn oxide due to each Elemental redistribution of cobalt magnesium manganese even, due to the embedding of magnesia key, transition element and lithium ion inconsistent phenomenon in material are eliminated, the layer structure of cobalt and manganese oxide is more stable, the electrical property of the lithium battery anode like this made by it is excellent, discharge platform is not easy decay, resistance to large current density and charge and discharge excessively, long service life.
Further improvement is, the total concentration of cobalt ions, magnesium ion and manganese ion in the described reaction solution that described step (1) is prepared is 50 ~ 120g/l, and described cobalt salt, magnesium salts and manganese salt are 1000:1 ~ 15 with the ratio of the total weight of described slow control agent.
Further improvement is, cobalt salt, magnesium salts and manganese salt described in described step (1) and the mixed mixing time of described slow control agent are 1 ~ 3h.In order to make slow control agent better form complex state with cobalt ions, manganese ion, magnesium ion, usually stirring 1 ~ 3h by after the aqueous solution of slow control agent and cobalt salt, magnesium salts, manganese salt, guaranteeing that the cobalt salt in solution, magnesium salts, manganese salt are controlled agent and fully contacted with delaying.
Further improvement is, the described slow control agent in described step (1) is citric acid C
6h
8o
7or/and 2 ethyl hexanoic acid; 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 manganese salt is one or more mixing of cobalt chloride, manganese nitrate, manganese sulfate.All without containing amine groups in the slow control agent citric acid adopted and 2 ethyl hexanoic acid oxalic 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, the described precipitation reagent in described step (2) is that NaOH is or/and potassium hydroxide.
Further improvement is, in described step (2), the time of purification process is 2 ~ 10h.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 speed that described in described step (3), reaction solution adds in reaction vessel is 1 ~ 3L/h, and the speed that described precipitation reagent adds in reaction vessel is simultaneously 0.5 ~ 1L/h; And guarantee that described reaction solution and described precipitation reagent are in radial and axial motion in described reaction vessel, pH keeps 9 ~ 12, reaction temperature is 89 ~ 100 DEG C, reaction time is 8 ~ 20h, make cobalt ions, magnesium ion, manganese ion under the effect of slow control agent, co-precipitation equably, forms slurry.The speed of adding reaction solution and precipitation reagent in reaction vessel should control in certain limit, the excessive velocities that precipitation reagent adds, and 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.
Further improvement is, the temperature of the water in described step (4) 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 that generates in course of reaction or potassium base organic substance; 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 (5), spherical for described class cobalt magnesium manganese hydroxide matrix is put into tray dryer machine, temperature is set to 110 ~ 230 DEG C, pressure is 0 ~ 0.02Mpa, dry and heat setting under the air atmosphere condition of oxygen volumn concentration 15 ~ 20%, the reaction time is 1.5 ~ 3h.
Another technical problem that the present invention also will solve is, there is provided a kind of cobalt magnesium Mn oxide lattice, structure cell regular, the migration such as other atoms, ion, electronics evenly, thus improves the lithium ion power battery cathode persursor material cobalt magnesium Mn oxide of the chemical property 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 cobalt magnesium Mn oxide prepared by preparation method of above-mentioned lithium-ion-power cell cobalt magnesium Mn oxide is Co
xmn
ymg
zo
4, wherein: 0<X+Y+Z≤3, X > 0,0<X+Y<2,0<Z≤0.1.
Adopt technique scheme, the lithium-ion-power cell of the acquisition average grain diameter 8 ~ 15 μm of cobalt magnesium Mn oxide, tap density 2.2 ~ 2.8g/cm
3; The mol ratio of cobalt, magnesium, manganese is 2 ~ 9:0.05 ~ 1:0.5 ~ 8.
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 embed magnesium atom by stable between cobalt, manganese, oxygen atom, increase for solving active cobalt atom content in material, the stability of the layer structure of cobalt/cobalt oxide and the layer structure of manganese trivalent and have found desirable approach; The lithium-ion-power cell cobalt magnesium Mn oxide obtained be colorless and odorless citric acid or with 2 ethyl hexanoic acid mixture system in synthesize, be process for cleanly preparing, and each Elemental redistribution of cobalt magnesium manganese is even, the COD process of wastewater treatment process is simply; And without follow-up mixed processes, energy consumption is low; The cobalt magnesium Mn oxide lattice prepared, structure cell are regular, and the migration such as other atoms, ion, electronics evenly, thus improves the chemical property 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 cobalt and manganese oxide;
Fig. 4 is the stereoscan photograph that magnesium types cobalt and manganese oxide mixed by existing machinery;
Fig. 5 is the grain size distribution of embodiment one;
Fig. 6 is the grain size distribution of existing cobalt and manganese oxide;
Fig. 7 is the grain size distribution that magnesium types cobalt and manganese oxide mixed by existing machinery.
Embodiment
Embodiment one: this lithium-ion-power cell preparation method of cobalt magnesium Mn oxide, adopt coprecipitation preparation, concrete steps are as follows:
(1) reaction solution is prepared: in 1200ml water, add cobalt chloride 1039.5g respectively, magnesium chloride 9.6g and manganese chloride 239.3g, fully mixes, and adds 1.8g citric acid C
6h
8o
7slow control agent is carried out stirring 1h and is mixed, obtained reaction solution;
(2) purification process: reaction solution is carried out purified treatment in without the box ultrafiltration container of magnetic, and the processing time is 5h, the reaction solution after being purified; Precipitation reagent 40% sodium hydroxide solution is purified in without the box ultrafiltration container of magnetic, the precipitation reagent after being purified;
(3) coprecipitation 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 axial flow, radial flow concurrently, control reaction temperature is 90 DEG C, pH value 9.5 ~ 10, and the reaction time is 16h; Make cobalt, magnesium, manganese 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, and obtaining average grain diameter is the spherical cobalt magnesium manganese ternary hydroxide of 12 μm, the slurry of inorganic salt mixt;
(4) removal of impurities process: this slurry removes inorganic salts, slow control agent in 90 DEG C of aqueous systems, obtained spherical cobalt magnesium manganese ternary hydroxide matrix;
(5) heat setting process: this spherical cobalt magnesium manganese ternary hydroxide matrix is put into tray dryer machine, 220 ± 5 DEG C, oxygen content is in the air of 18 ± 1%, 0.01Mpa pressure (gauge pressure), reaction time is that 2h carries out anhydrating and hot reconstruction processing, obtains tap density 2.6g/cm
3, average grain diameter 11.5 μm power lithium-ion battery positive electrode material precursor cobalt magnesium Mn oxide (cobalt, magnesium, manganese mol ratio are 8:0.1:1.9), 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 |
| Cobalt (Co) | wt％ | 60.064 |
| Magnesium (Mg) | wt％ | 0.307 |
| Manganese (Mn) | wt％ | 12.615 |
| Iron (Fe) | wt％ | 0.0008 |
| Copper (Cu) | wt％ | No |
| Chromium (Cr) | wt％ | No |
| Sodium (Na) | wt％ | 0.0240 |
| Plumbous (Pb) | wt％ | 0.0028 |
| Magnetic foreign body | BBP | 31 |
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 cobalt magnesium Mn oxide, adopt coprecipitation preparation, concrete steps are as follows:
(1) prepare reaction solution: in 3000ml water, add cobalt chloride 649.7g respectively, magnesium chloride 8.6g and manganese chloride 674.2g, fully mixes, and to add 2.2g weight ratio be 2:1 citric acid C
6h
8o
7, 2 ethyl hexanoic acid H
18c
8o
2mixture carries out stirring 2.5h and mixes, obtained reaction solution;
(2) purification process: reaction solution is carried out purified treatment in without the box ultrafiltration container of magnetic, and the processing time is 2h, the reaction solution after being purified; Precipitation reagent 40% sodium hydroxide solution is purified in without the box ultrafiltration container of magnetic, the precipitation reagent after being purified;
(3) coprecipitation reaction: by reaction solution with the speed of 1.8L/h, precipitation reagent enters without in magnetic response still with the Rate Dispersion of 0.82L/h simultaneously, controls reaction temperature 95 DEG C in the liquid phase environment having axial flow, radial flow concurrently; PH value 9.5 ~ 10, reaction time is 10h, make cobalt, magnesium, manganese 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, obtains spherical cobalt magnesium manganese ternary hydroxide, inorganic salt mixt slurry that average grain diameter is 11.5 μm;
(4) removal of impurities process: this slurry removes inorganic salts, slow control agent in 95 DEG C of aqueous systems, obtained spherical cobalt magnesium manganese ternary hydroxide matrix;
(5) heat setting process: this spherical cobalt magnesium manganese ternary hydroxide matrix is put into tray dryer machine, 220 ± 5 DEG C, oxygen content is in the air of 18 ± 1%, 0.01Mpa pressure (gauge pressure), reaction time is that 3h carries out anhydrating and hot reconstruction processing, obtains tap density 2.6g/cm
3, average grain diameter 11 μm power lithium-ion battery positive electrode material precursor cobalt magnesium Mn oxide (cobalt, magnesium, manganese mol ratio are 5:0.09:4.99).
Embodiment three: this lithium-ion-power cell preparation method of cobalt magnesium Mn oxide, adopt coprecipitation preparation, concrete steps are as follows:
(1) reaction solution is prepared: in 1900ml water, add cobalt chloride 520g respectively, magnesium chloride 3.2g and manganese chloride 752.2g, fully mixes, and adds 2.2g citric acid C
6h
8o
7carry out stirring 2h to mix, obtained reaction solution;
(2) purification process: reaction solution is carried out purified treatment in without the box ultrafiltration container of magnetic, and the processing time is 2h, the reaction solution after being purified; Precipitation reagent 40% sodium hydroxide solution is purified in without the box ultrafiltration container of magnetic, the precipitation reagent after being purified;
(3) coprecipitation reaction: by reaction solution with the speed of 1.5L/h, precipitation reagent enters without in magnetic response still with the Rate Dispersion of 0.6L/h simultaneously, controls reaction temperature 90 DEG C in the liquid phase environment having axial flow, radial flow concurrently; PH value 10 ~ 10.5, reaction time is 11h, make cobalt, magnesium, manganese 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, obtains spherical cobalt magnesium manganese ternary hydroxide, inorganic salt mixt slurry that average grain diameter is 10 μm;
(4) removal of impurities process: this slurry removes inorganic salts, slow control agent in 85 DEG C of aqueous systems, obtained spherical cobalt magnesium manganese ternary hydroxide matrix;
(5) heat setting process: this spherical cobalt magnesium manganese ternary hydroxide matrix is put into tray dryer machine, 220 ± 5 DEG C, oxygen content is in the air of 18 ± 1%, 0.01Mpa pressure (gauge pressure), reaction time is that 1.5h carries out anhydrating and hot reconstruction processing, obtains tap density 2.7g/cm
3, average grain diameter 9.5 μm power lithium-ion battery positive electrode material precursor cobalt magnesium Mn oxide (cobalt, magnesium, manganese mol ratio are 4:0.03:5.97).
Embodiment four: this lithium-ion-power cell preparation method of cobalt magnesium Mn oxide, adopt coprecipitation preparation, concrete steps are as follows:
(1) prepare reaction solution: in 4000ml water, add cobalt chloride 488g respectively, magnesium chloride 4.77g and manganese chloride 781g, fully mixes, and to add 3.5g weight ratio be 2:1 citric acid C
6h
8o
7, 2 ethyl hexanoic acid H
18c
8o
2mixture carries out stirring 3h and mixes, obtained reaction solution;
(2) purification process: reaction solution is carried out purified treatment in without the box ultrafiltration container of magnetic, and the processing time is 2.5h, the reaction solution after being purified; Precipitation reagent 30% potassium hydroxide solution is purified in without the box ultrafiltration container of magnetic, the precipitation reagent after being purified;
(3) coprecipitation reaction: by reaction solution with the speed of 1.5L/h, precipitation reagent enters without in magnetic response still with the Rate Dispersion of 0.7L/h simultaneously, controls reaction temperature 95 DEG C in the liquid phase environment having axial flow, radial flow concurrently; PH value 9.5 ~ 10, reaction time is 10.5h, make cobalt, magnesium, manganese 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, obtains spherical cobalt magnesium manganese ternary hydroxide, inorganic salt mixt slurry that average grain diameter is 10.5 μm;
(4) removal of impurities process: this slurry removes inorganic salts, slow control agent in 95 DEG C of aqueous systems, obtained spherical cobalt magnesium manganese ternary hydroxide matrix;
(5) heat setting process: this spherical cobalt magnesium manganese ternary hydroxide matrix is put into tray dryer machine, 220 ± 5 DEG C, oxygen content is in the air of 18 ± 1%, 0.01Mpa pressure (gauge pressure), reaction time is that 2.5h carries out anhydrating and hot reconstruction processing, obtains tap density 2.7g/cm
3, average grain diameter 10 μm power lithium-ion battery positive electrode material precursor cobalt magnesium Mn oxide (cobalt, magnesium, manganese mol ratio are 3.75:0.05:6.2).
Embodiment five: this lithium-ion-power cell preparation method of cobalt magnesium Mn oxide, adopt coprecipitation preparation, concrete steps are as follows:
(1) reaction solution is prepared: in 1500ml water, add cobalt chloride 520g respectively, magnesium chloride 5.8g and manganese chloride 748g, fully mixes, and adds 1.5g citric acid C
6h
8o
7carry out stirring 1.5h to mix, obtained reaction solution;
(2) purification process: reaction solution is carried out purified treatment in without the box ultrafiltration container of magnetic, and the processing time is 3h, the reaction solution after being purified; Precipitation reagent 30% potassium hydroxide solution is purified in without the box ultrafiltration container of magnetic, the precipitation reagent after being purified;
(3) coprecipitation reaction: by reaction solution with the speed of 1.7L/h, precipitation reagent enters without in magnetic response still with the Rate Dispersion of 0.7L/h simultaneously, controls reaction temperature 90 DEG C in the liquid phase environment having axial flow, radial flow concurrently; PH value 10 ~ 10.5, reaction time is 12h, make cobalt, magnesium, manganese 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, obtains spherical cobalt magnesium manganese ternary hydroxide, inorganic salt mixt slurry that average grain diameter is 11 μm;
(4) removal of impurities process: this slurry removes inorganic salts, slow control agent in 90 DEG C of aqueous systems, obtained spherical cobalt magnesium manganese ternary hydroxide matrix;
(5) heat setting process: this spherical cobalt magnesium manganese ternary hydroxide matrix is put into tray dryer machine, 220 ± 5 DEG C, oxygen content is in the air of 18 ± 1%, 0.01Mpa pressure (gauge pressure), reaction time is that 2h carries out anhydrating and hot reconstruction processing, obtains tap density 2.7g/cm
3, average grain diameter 10 μm power lithium-ion battery positive electrode material precursor cobalt magnesium Mn oxide (cobalt, magnesium, manganese mol ratio are 4:0.06:5.94).
Embodiment six: this lithium-ion-power cell preparation method of cobalt magnesium Mn oxide, adopt coprecipitation preparation, concrete steps are as follows:
(1) reaction solution is prepared: in 2500ml water, add cobalt chloride 779.6g respectively, magnesium chloride 3.8g and manganese chloride 498.7g, fully mixes, and adds 2.5g citric acid C
6h
8o
7carry out stirring 2.5h to mix, obtained reaction solution;
(2) purification process: reaction solution is carried out purified treatment in without the box ultrafiltration container of magnetic, and the processing time is 4h, the reaction solution after being purified; Precipitation reagent 40% sodium hydroxide solution is purified in without the box ultrafiltration container of magnetic, the precipitation reagent after being purified;
(3) coprecipitation reaction: by reaction solution with the speed of 1.8L/h, precipitation reagent enters without in magnetic response still with the Rate Dispersion of 0.8L/h simultaneously, controls reaction temperature 90 DEG C in the liquid phase environment having axial flow, radial flow concurrently; PH value 9.8 ~ 10.3, reaction time is 14h, make cobalt, magnesium, manganese 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, obtains spherical cobalt magnesium manganese ternary hydroxide, inorganic salt mixt slurry that average grain diameter is 13 μm;
(4) removal of impurities process: this slurry removes inorganic salts, slow control agent in 95 DEG C of aqueous systems, obtained spherical cobalt magnesium manganese ternary hydroxide matrix;
(5) heat setting process: this spherical cobalt magnesium manganese ternary hydroxide matrix is put into tray dryer machine, 220 ± 5 DEG C, oxygen content is in the air of 18 ± 1%, 0.01Mpa pressure (gauge pressure), reaction time is that 2.5h carries out anhydrating and hot reconstruction processing, obtains tap density 2.8g/cm
3, average grain diameter 12.5 μm power lithium-ion battery positive electrode material precursor cobalt magnesium Mn oxide (cobalt, magnesium, manganese mol ratio are 6:0.04:3.96).
Embodiment seven: this lithium-ion-power cell preparation method of cobalt magnesium Mn oxide, adopt coprecipitation preparation, concrete steps are as follows:
(1) prepare reaction solution: in 3500ml water, add cobalt chloride 1169.4g respectively, magnesium chloride 5.34g and manganese chloride 119.7g, fully mixes, and to add 3.3g weight ratio be 2:1 citric acid C
6h
8o
7, 2 ethyl hexanoic acid H
18c
8o
2mixture carries out stirring 3h and mixes, obtained reaction solution;
(2) purification process: reaction solution is carried out purified treatment in without the box ultrafiltration container of magnetic, and the processing time is 5h, the reaction solution after being purified; Precipitation reagent 30% potassium hydroxide solution is purified in without the box ultrafiltration container of magnetic, the precipitation reagent after being purified;
(3) coprecipitation reaction: by reaction solution with the speed of 1.9L/h, precipitation reagent enters without in magnetic response still with the Rate Dispersion of 0.85L/h simultaneously, controls reaction temperature 95 DEG C in the liquid phase environment having axial flow, radial flow concurrently; PH value 9.5 ~ 10, reaction time is 16h, make cobalt, magnesium, manganese 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, obtains spherical cobalt magnesium manganese ternary hydroxide, inorganic salt mixt slurry that average grain diameter is 10.5 μm;
(4) removal of impurities process: this slurry removes inorganic salts, slow control agent in 85 DEG C of aqueous systems, obtained spherical cobalt magnesium manganese ternary hydroxide matrix;
(5) heat setting process: this spherical cobalt magnesium manganese ternary 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), reaction time is that 2h carries out anhydrating and hot reconstruction processing, obtains tap density 2.8g/cm
3, average grain diameter 10 μm power lithium-ion battery positive electrode material precursor cobalt magnesium Mn oxide (cobalt, magnesium, manganese mol ratio are 9:0.05:0.95).
Embodiment eight: this lithium-ion-power cell preparation method of cobalt magnesium Mn oxide, adopt coprecipitation preparation, concrete steps are as follows:
(1) prepare reaction solution: in 3500ml water, add cobalt nitrate 1420.6g respectively, magnesium nitrate 1.7g and manganese nitrate 535.2g, fully mixes, and to add 3.2g weight ratio be 2:1 citric acid C
6h
8o
7, 2 ethyl hexanoic acid H
18c
8o
2mixture carries out stirring 2.5h and mixes, obtained reaction solution;
(2) purification process: reaction solution is carried out purified treatment in without the box ultrafiltration container of magnetic, and the processing time is 6h, the reaction solution after being purified; Precipitation reagent 40% sodium hydroxide solution is purified in without the box ultrafiltration container of magnetic, the precipitation reagent after being purified;
(3) coprecipitation reaction: by reaction solution with the speed of 1.8L/h, precipitation reagent enters without in magnetic response still with the Rate Dispersion of 0.8L/h simultaneously, controls reaction temperature 92 DEG C in the liquid phase environment having axial flow, radial flow concurrently; PH value 9.8 ~ 10.2, reaction time is 18h, make cobalt, magnesium, manganese 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, obtains spherical cobalt magnesium manganese ternary hydroxide, inorganic salt mixt slurry that average grain diameter is 9.5 μm;
(4) removal of impurities process: this slurry removes inorganic salts, slow control agent in 90 DEG C of aqueous systems, obtained spherical cobalt magnesium manganese ternary hydroxide matrix;
(5) heat setting process: this spherical cobalt magnesium manganese ternary hydroxide matrix is put into tray dryer machine, 220 ± 5 DEG C, oxygen content is in the air of 18 ± 1%, 0.01Mpa pressure (gauge pressure), reaction time is that 2h carries out anhydrating and hot reconstruction processing, obtains tap density 2.6g/cm
3, average grain diameter 9.2 μm power lithium-ion battery positive electrode material precursor cobalt magnesium Mn oxide (cobalt, magnesium, manganese mol ratio are 7:0.01:2.99).
Embodiment nine: this lithium-ion-power cell preparation method of cobalt magnesium Mn oxide, adopt coprecipitation preparation, concrete steps are as follows:
(1) prepare reaction solution: in 3000ml water, add cobalt nitrate 406g respectively, magnesium nitrate 8.4g and manganese nitrate 1504g, fully mixes, and to add 3.0g weight ratio be 2:1 citric acid C
6h
8o
7, 2 ethyl hexanoic acid H
18c
8o
2mixture carries out stirring 2.5h and mixes, obtained reaction solution;
(2) purification process: reaction solution is carried out purified treatment in without the box ultrafiltration container of magnetic, and the processing time is 5h, the reaction solution after being purified; Precipitation reagent 30% potassium hydroxide solution is purified in without magnetic box ultrafiltration container filter, the precipitation reagent after being purified;
(3) coprecipitation reaction: by reaction solution with the speed of 1.8L/h, precipitation reagent enters without in magnetic response still with the Rate Dispersion of 0.8L/h simultaneously, controls reaction temperature 98 DEG C in the liquid phase environment having axial flow, radial flow concurrently; PH value 10 ~ 10.5, reaction time is 16h, make cobalt, magnesium, manganese 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, obtains spherical cobalt magnesium manganese ternary hydroxide, inorganic salt mixt slurry that average grain diameter is 10 μm;
(4) removal of impurities process: this slurry removes inorganic salts, slow control agent in 95 DEG C of aqueous systems, obtained spherical cobalt magnesium manganese ternary hydroxide matrix;
(5) heat setting process: this spherical cobalt magnesium manganese ternary hydroxide matrix is put into tray dryer machine, 220 ± 5 DEG C, oxygen content is in the air of 18 ± 1%, 0.01Mpa pressure (gauge pressure), reaction time is that 2h carries out anhydrating and hot reconstruction processing, obtains tap density 2.6g/cm
3, average grain diameter 9.5 μm power lithium-ion battery positive electrode material precursor cobalt magnesium Mn oxide (cobalt, magnesium, manganese mol ratio are 2:0.05:7.95).
Embodiment ten: this lithium-ion-power cell preparation method of cobalt magnesium Mn oxide, adopt coprecipitation preparation, concrete steps are as follows:
(1) prepare reaction solution: in 4500ml water, add cobalt nitrate 548.8g respectively, magnesium nitrate 6.7g and manganese nitrate 1242.2g, fully mixes, and to add 3.5g weight ratio be 2:1 citric acid C
6h
8o
7, 2 ethyl hexanoic acid H
18c
8o
2mixture carries out stirring 3h and mixes, obtained reaction solution;
(2) purification process: reaction solution is carried out purified treatment in without the box ultrafiltration container of magnetic, and the processing time is 6h, the reaction solution after being purified; Precipitation reagent 40% sodium hydroxide solution is purified in without the box ultrafiltration container of magnetic, the precipitation reagent after being purified;
(3) coprecipitation reaction: by reaction solution with the speed of 2L/h, precipitation reagent enters without in magnetic response still with the Rate Dispersion of 0.9L/h simultaneously, controls reaction temperature 90 DEG C in the liquid phase environment having axial flow, radial flow concurrently; PH value 9.5 ~ 10, reaction time is 20h, make cobalt, magnesium, manganese 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, obtains spherical cobalt magnesium manganese ternary hydroxide, inorganic salt mixt slurry that average grain diameter is 11.5 μm;
(4) removal of impurities process: this slurry removes inorganic salts, slow control agent in 80 DEG C of aqueous systems, obtained spherical cobalt magnesium manganese ternary hydroxide matrix;
(5) heat setting process: this spherical cobalt magnesium manganese ternary hydroxide matrix is put into tray dryer machine, 220 ± 5 DEG C, oxygen content is in the air of 18 ± 1%, 0.01Mpa pressure (gauge pressure), reaction time is that 2h carries out anhydrating and hot reconstruction processing, obtains tap density 2.8g/cm
3, average grain diameter 11 μm power lithium-ion battery positive electrode material precursor cobalt magnesium Mn oxide (cobalt, magnesium, manganese mol ratio are 3:0.04:6.94).
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 cobalt magnesium Mn oxide, is characterized in that, this lithium-ion-power cell cobalt magnesium Mn oxide adopts coprecipitation preparation, and concrete steps are as follows:
(1) prepare reaction solution: get a certain proportion of cobalt salt, magnesium salts and manganese salt water-soluble, form the mixed aqueous solution of cobalt salt, magnesium salts and manganese salt; In described mixed aqueous solution, add slow control agent mix and stir and make it mix, obtain reaction solution;
(2) purification process: the precipitation reagent needed for the reaction solution prepared in step (1) and reaction is put into carry out purified treatment without the box ultrafiltration container of magnetic respectively;
(3) coprecipitation reaction: the reaction solution in step (2) after purification process and precipitation reagent are added in reaction vessel simultaneously and carry out precipitation reaction, co-precipitation equably, forms slurry; Described reaction vessel is the reaction vessel having radial flow and axial flow concurrently;
(4) removal of impurities process: the slurry obtained in step (3) is repeatedly embathed in water, the impurity such as removing inorganic salts, slow control agent, obtain class spherical cobalt magnesium manganese hydroxide matrix;
(5) heat setting process: institute's class that obtains spherical cobalt magnesium manganese hydroxide matrix in step (4) is carried out drying and heat setting process, thus obtains lithium-ion-power cell cobalt magnesium Mn oxide.
2. the preparation method of lithium-ion-power cell cobalt magnesium Mn oxide according to claim 1, it is characterized in that, the total concentration of cobalt ions, magnesium ion and manganese ion in the described reaction solution that described step (1) is prepared is 50 ~ 120g/l, and described cobalt salt, magnesium salts and manganese salt are 1000:1 ~ 15 with the ratio of the total weight of described slow control agent.
3. the preparation method of lithium-ion-power cell cobalt magnesium Mn oxide according to claim 1, is characterized in that, cobalt salt, magnesium salts and manganese salt described in described step (1) and the mixed mixing time of described slow control agent are 1 ~ 3h.
4. the preparation method of cobalt magnesium Mn oxide of the lithium-ion-power cell according to Claims 2 or 3, is characterized in that, the described slow control agent in described step (1) is citric acid C
6h
8o
7or/and 2 ethyl hexanoic acid; 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 manganese salt is one or more mixing of cobalt chloride, manganese nitrate, manganese sulfate.
5. the preparation method of lithium-ion-power cell cobalt magnesium Mn oxide according to claim 4, is characterized in that, the described precipitation reagent in described step (2) is that NaOH is or/and potassium hydroxide.
6. the preparation method of lithium-ion-power cell cobalt magnesium Mn oxide according to claim 5, is characterized in that, in described step (2), the time of purification process is 2 ~ 10h.
7. the preparation method of lithium-ion-power cell cobalt magnesium Mn oxide according to claim 6, it is characterized in that, the speed that described in described step (3), reaction solution adds in reaction vessel is 1 ~ 3L/h, and the speed that described precipitation reagent adds in reaction vessel is simultaneously 0.5 ~ 1L/h; And guaranteeing that described reaction solution and described precipitation reagent are in radial and axial motion in described reaction vessel, pH keeps 9 ~ 12, and reaction temperature is 89 ~ 100 DEG C, and the reaction time is 8 ~ 15h; Make cobalt ions, magnesium ion, manganese ion under the effect of slow control agent, co-precipitation equably, form slurry.
8. the preparation method of lithium-ion-power cell cobalt magnesium Mn oxide according to claim 7, is characterized in that, the temperature of the water in described step (4) removal of impurities process is 85 ~ 95 DEG C.
9. the preparation method of lithium-ion-power cell cobalt magnesium Mn oxide according to claim 7, it is characterized in that, in described step (5), spherical for described class cobalt magnesium manganese hydroxide matrix is put into tray dryer machine, temperature is set to 110 ~ 230 DEG C, pressure is 0 ~ 0.02Mpa, dry and heat setting under the air atmosphere condition of oxygen volumn concentration 15 ~ 20%, the reaction time is 1.5 ~ 3h.
10. one kind adopts the lithium-ion-power cell cobalt magnesium Mn oxide prepared by the preparation method of the cobalt magnesium Mn 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 cobalt magnesium Mn oxide of acquisition is Co
xmn
ymg
zo
4, wherein: 0<X+Y+Z≤3, X > 0,0<X+Y<2,0<Z≤0.1.
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