CN105140499A - Preparation method of Co-Mg oxide for lithium-ion power battery - Google Patents
Preparation method of Co-Mg oxide for lithium-ion power battery Download PDFInfo
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- CN105140499A CN105140499A CN201510385025.2A CN201510385025A CN105140499A CN 105140499 A CN105140499 A CN 105140499A CN 201510385025 A CN201510385025 A CN 201510385025A CN 105140499 A CN105140499 A CN 105140499A
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Abstract
The invention relates to a preparation method of a Co-Mg oxide for a lithium-ion power battery. A co-precipitation method is adopted, and the preparation method comprises the following steps of: (1) generating a complex; (2) carrying out purification treatment; (3) carrying out co-precipitation reaction; (4) carrying out impurity removal; (5) drying and stabilizing; and (6) carrying out reconstruction optimization. A chemical precipitation reaction of a certain mole concentration of a cobalt 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 on the conditions of a certain temperature, a flow rate, a pH value, a stirring speed and the like and in a mixture system with the presence of a stabilizer so as to form an atomic-scale uniform mixture of cobalt hydroxide and magnesium hydrate to be deposited, and then low-temperature drying and dewatering and high-temperature reconstruction are carried out to form the Co-Mg oxide, the molecular formula of the Co-Mg oxide is Co<X>Mg<1-X>O2, and X is more than or equal to 0.9 but less than 1.
Description
Technical field
The present invention relates to lithium-ion-power cell technical field, i.e. the preparation method of wherein a kind of lithium dynamical battery cobalt magnesium oxide.
Background technology
Along with market is to the active demand of personalized lithium ion battery, the expert of association area more and more payes attention to the exploitation of the New Technologies of clean energy resource and energy storage material.Personalized 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 personalized power lithium-ion battery positive electrode used and presoma thereof.
Current common motive power 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, mix magnesium cobaltosic oxide 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 oxide preparation method for these technology: the blending of (1) machinery is uneven, obtained material still cannot eliminate transition elements as the inconsistent phenomenon brought between cobalt etc. and lithium ion, crystal structure is still unstable, lattice is easily out of shape, so that other atom, electronics, Ion transfer is difficult or uneven, (2) resulting materials is also because transition elements is as cobalt etc. and the dislocation of lithium ion, and cause the chemical properties such as capability retention is low, platform decay is fast poor, useful life is short, (3) the wet-layer preparation process had produces environmentally harmful ammonia (NH3), ammonia nitriding compound (NH+) etc., (4) 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 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 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: this lithium-ion-power cell cobalt magnesium oxide adopts coprecipitation preparation, and concrete steps are as follows:
(1) generate complex compound: get a certain proportion of cobalt salt and magnesium salts water-soluble, form the mixed aqueous solution of cobalt salt and magnesium salts; In described mixed aqueous solution, add stabilizer mix and stir and make it mix, obtain the reaction solution with complex compound;
(2) purification process: the precipitation reagent needed for the reaction solution with complex compound obtained in step (1) and reaction is put into carry out purified treatment without the box drainer 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, impurity such as removing inorganic salts, stabilizer etc., obtains class spherical cobalt magnesium hydroxide matrix;
(5) dry qualitative: institute's class that obtains spherical cobalt magnesium hydroxide matrix in step (4) to be carried out drying at a certain temperature in air atmosphere qualitative;
(6) reconstruction and optimization: institute's class that obtains spherical cobalt magnesium hydroxide matrix in step (5) is carried out high-temperature reconstruction optimization, thus obtains lithium-ion-power cell cobalt magnesium oxide.
Adopt technique scheme, the cobalt salt of certain molar concentration, magnesium salts 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 stabilizer, in the reaction vessel having radial flow and axial flow concurrently, carry out chemical precipitation reaction with precipitation reagent, thus formed cobalt hydroxide, magnesium hydroxide atom level homogeneous mixture and precipitate, then dewatered by low temperature drying, high-temperature reconstruction is optimized, and define cobalt magnesium oxide, molecular formula is Co
xmg
(1-X)o
2(0.9≤X<1); First complex compound is defined by stabilizer and cobalt salt, magnesium salts 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 oxide; The Main Function of purification process is the chemical property being conducive to the stable of subsequent reactions and improving subsequent product; This preparation method eliminates the problem because of transition metal cobalt ions and the dislocation of lithium ion and the less unit cell volume of cobalt/cobalt oxide by homogeneous phase embedding magnesium atom replacement part cobalt atom; And eliminate because magnesium elements introduces the cobalt ions quantity reduced by raising tap density and specific energy; Thus improve the chemical properties such as oxygen cobalt lithium series lithium ion battery volume and capacity ratio, cycle life, high-temperature stability; Obtained lithium-ion-power cell cobalt magnesium oxide due to each Elemental redistribution of cobalt magnesium even, due to the embedding of magnesia key, transition element and lithium ion inconsistent phenomenon in material are eliminated, and the cobalt lithium ion quantity that can misplace with lithium ion reduces, 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.Adopt technique scheme, the lithium-ion-power cell of the acquisition average grain diameter 8 ~ 15 μm of cobalt magnesium oxide, tap density 2.2 ~ 2.8g/cm
3; The mol ratio of cobalt, magnesium is 9 ~ 10:0.1 ~ 3.
Further improvement is, the described stabilizer in described step (1) is citric acid C
6h
8o
7or/and butanedioic acid C
4h
6o
4; 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.The cobalt salt adopted and magnesium salts are all no side effectses, the stabilizer citric acid adopted and butanedioic acid C
4h
6o
4in all without containing amine groups, 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 cobalt ions in the described reaction solution that described step (1) is prepared and the total concentration of magnesium ion are 40 ~ 130g/l, and described cobalt salt and magnesium salts are 100:1 ~ 1.5 with the ratio of the total weight of described stabilizer.
Further improvement is, cobalt salt described in described step (1) and magnesium salts and the mixed mixing time of described stabilizer are 1 ~ 3h.In order to make stabilizer better and cobalt salt, magnesium salts form complex state, usually stir 1 ~ 3h by after the aqueous solution of stabilizer and cobalt salt, magnesium salts, guarantee the cobalt salt in solution, magnesium salts fully contacts with stabilizer.
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 ~ 6h.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 ~ 2L/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, radial flow is 300 ~ 400 turns/min, and axial flow is 500 ~ 600 turns/min; Regulate pH to be 9 ~ 12, reaction temperature is 70 ~ 85 DEG C, and the reaction time is 10 ~ 20h; Make cobalt ions and magnesium ion under the effect of stabilizer, co-precipitation equably, form slurry.The material that precipitation reaction must be guaranteed in reaction vessel is in the radial direction of High Linear cutting force and over haulage to turbulent motion environment; And must carry out in the system of superpower multidimensional, guarantee that feed liquid is disperseed rapidly and is that uniform particles is grown up creation environment; Therefore, the speed of radial flow and axial flow is controlled; The speed of adding reaction solution and precipitation reagent in this export-oriented 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 also the pH value in order to regulate 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, some impurity that all may cause too high or too low for temperature of water in removal of impurities process cannot be removed, and this temperature end, can by a small amount of sodium base of generating in course of reaction or potassium base organic substance at this temperature, easily clean up.
Further improvement is, in described step (5), spherical for described class cobalt magnesium hydroxide matrix is put into drying box, 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.
Further improvement is, class spherical cobalt magnesium hydroxide matrix after qualitative to drying in described step (6) is 550 ~ 700 DEG C in reaction temperature, pressure is 0 ~ 0.02Mpa, oxygen volumn concentration is be reconstructed optimization in the air atmosphere of 15 ~ 20%, and the reaction time is 15 ~ 25h.
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, the cobalt magnesium oxide lattice prepared, structure cell are regular, stop the formation of unstable Co-Co support, other atoms, ion, electronics etc. are embedding evenly de-, thus improve the chemical property of corresponding product, the stability of structure; The lithium-ion-power cell cobalt magnesium oxide obtained be colorless and odorless citric acid or with butanedioic acid mixture system in synthesize, be process for cleanly preparing, and cobalt magnesium Was Used is evenly distributed, the COD process of wastewater treatment process is simple; And without follow-up mixed processes, energy consumption is low.The cobalt magnesium 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 the invention process one;
Fig. 2 is the partial enlargement stereoscan photograph of the invention process one;
Fig. 3 is the stereoscan photograph of existing cobaltosic oxide;
Fig. 4 is the stereoscan photograph that magnesium types cobaltosic oxide mixed by existing machinery;
Fig. 5 is the grain size distribution of the invention process one;
Fig. 6 is the grain size distribution of existing cobaltosic oxide;
Fig. 7 is the grain size distribution that magnesium types cobaltosic oxide mixed by existing machinery.
Embodiment
Embodiment one: this lithium-ion-power cell preparation method of cobalt magnesium oxide, adopt coprecipitation preparation, concrete steps are as follows:
(1) complex compound is generated: in 3500ml water, add cobalt chloride 585g and magnesium chloride 47.7g respectively, fully mix, and add 2.2g citric acid C
6h
8o
7stabilizer carries out stirring 1h and mixes, the obtained reaction solution with complex compound;
(2) purification process: the reaction solution with complex compound is carried out purified treatment in without the box drainer of magnetic, and the processing time is 4h, the reaction solution after being purified; Precipitation reagent 25% sodium hydroxide solution is purified in without the box drainer of magnetic, the precipitation reagent after being purified;
(3) coprecipitation reaction: by reaction solution with the speed of 1.8L/h, precipitation reagent adds without in magnetic response still with the Rate Dispersion of 0.9L/h simultaneously, in the liquid phase environment having axial flow (300 turns per minute), radial flow (520 turns per minute) concurrently, control reaction temperature is 75 DEG C, regulate pH value 10 ~ 11, the reaction time is 15h; Make cobalt, magnesium 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 hydroxide of 18 μm, the slurry of inorganic salt mixt;
(4) removal of impurities process: this slurry removes inorganic salts, stabilizer in 90 DEG C of aqueous systems, obtained spherical cobalt magnesium hydroxide matrix;
(5) dry qualitative: this spherical cobalt magnesium hydroxide matrix is put into drying machine, 110 ± 5 DEG C, oxygen content is in the air of 18 ± 1%, 0.1Mpa pressure (gauge pressure), it is dry and qualitative that the reaction time is that 2h carries out anhydrating;
(6) reconstruction and optimization: by anhydrate dry and qualitative after spherical cobalt magnesium hydroxide matrix immigration calciner in be reconstructed optimization, reaction temperature is 580 ± 5 DEG C, 0.1Mpa pressure (gauge pressure), oxygen content be in the air of 18 ± 1% processing time be 20h, obtain tap density 2.6g/cm
3, average grain diameter 17.8 μm power lithium-ion battery positive electrode material precursor cobalt magnesium oxide (cobalt, magnesium mol ratio are 9:1), 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％ | 72.91 |
| Magnesium (Mg) | wt％ | 0.300 |
| Iron (Fe) | wt％ | 0.0011 |
| Copper (Cu) | wt％ | No |
| Chromium (Cr) | wt％ | No |
| Sodium (Na) | wt％ | 0.0210 |
| Plumbous (Pb) | wt％ | 0.0020 |
| Magnetic foreign body | BBP | 35 |
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 oxide, adopt coprecipitation preparation, concrete steps are as follows:
(1) complex compound is generated: in 3500ml water, add cobalt chloride 617.2g and magnesium chloride 23.9g respectively, fully mix, and add the citric acid C that 2.0g weight ratio is 2:1
6h
8o
7with butanedioic acid C
4h
6o
4stabilized with mixture agent is carried out stirring 2.5h and is mixed, the obtained reaction solution with complex compound;
(2) purification process: the reaction solution with complex compound is carried out purified treatment in without the box drainer of magnetic, and the processing time is 3h, the reaction solution after being purified; Precipitation reagent 25% sodium hydroxide solution is purified in without the box drainer of magnetic, the precipitation reagent after being purified;
(3) coprecipitation 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 axial flow (320 turns per minute), radial flow (520 turns per minute) concurrently, control reaction temperature is 70 DEG C, regulate pH value 10 ~ 11, the reaction time is 14h; Make cobalt, magnesium 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 hydroxide of 18.2 μm, the slurry of inorganic salt mixt;
(4) removal of impurities process: this slurry removes inorganic salts, stabilizer in 95 DEG C of aqueous systems, obtained spherical cobalt magnesium hydroxide matrix;
(5) dry qualitative: this spherical cobalt magnesium hydroxide matrix is put into drying machine, 110 ± 5 DEG C, oxygen content is in the air of 18 ± 1%, 0.1Mpa pressure (gauge pressure), it is dry and qualitative that the reaction time is that 3h carries out anhydrating;
(6) reconstruction and optimization: by anhydrate dry and qualitative after spherical cobalt magnesium hydroxide matrix immigration calciner in be reconstructed optimization, reaction temperature is 600 ± 5 DEG C, 0.1Mpa pressure (gauge pressure), oxygen content be in the air of 18 ± 1% processing time be 20h, obtain tap density 2.8g/cm
3, average grain diameter 18 μm power lithium-ion battery positive electrode material precursor cobalt magnesium oxide (cobalt, magnesium mol ratio are 9.5:0.5).
Embodiment three: this lithium-ion-power cell preparation method of cobalt magnesium oxide, adopt coprecipitation preparation, concrete steps are as follows:
(1) complex compound is generated: in 2900ml water, add cobalt chloride 593.6g and magnesium chloride 6.7g respectively, fully mix, and add 2.0g butanedioic acid C
4h
6o
4stabilizer carries out stirring 2h and mixes, the obtained reaction solution with complex compound;
(2) purification process: the reaction solution with complex compound is carried out purified treatment in without the box drainer of magnetic, and the processing time is 12h, the reaction solution after being purified; Precipitation reagent 25% sodium hydroxide solution is purified in without the box drainer 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 0.7L/h simultaneously, in the liquid phase environment having axial flow (350 turns per minute), radial flow (500 turns per minute) concurrently, control reaction temperature is 75 DEG C, regulate pH value 10.5 ~ 11.5, the reaction time is 12h; Make cobalt, magnesium 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 hydroxide of 18.5 μm, the slurry of inorganic salt mixt;
(4) removal of impurities process: this slurry removes inorganic salts, stabilizer in 85 DEG C of aqueous systems, obtained spherical cobalt magnesium hydroxide matrix;
(5) dry qualitative: this spherical cobalt magnesium hydroxide matrix is put into drying machine, 120 ± 5 DEG C, oxygen content is in the air of 18 ± 1%, 0.1Mpa pressure (gauge pressure), it is dry and qualitative that the reaction time is that 1.5h carries out anhydrating;
(6) reconstruction and optimization: by anhydrate dry and qualitative after spherical cobalt magnesium hydroxide matrix immigration calciner in be reconstructed optimization, reaction temperature is 620 ± 5 DEG C, 0.1Mpa pressure (gauge pressure), oxygen content be in the air of 18 ± 1% processing time be 18h, obtain tap density 2.7g/cm
3, average grain diameter 18.3 μm power lithium-ion battery positive electrode material precursor cobalt magnesium oxide (cobalt, magnesium mol ratio are 9.75:0.25).
Embodiment four: this lithium-ion-power cell preparation method of cobalt magnesium oxide, adopt coprecipitation preparation, concrete steps are as follows:
(1) complex compound is generated: in 4000ml water, add cobalt chloride 1234.4g and magnesium chloride 19.1g respectively, fully mix, and add the citric acid C that 3.0g weight ratio is 2:1
6h
8o
7with butanedioic acid C
4h
6o
4stabilized with mixture agent is carried out stirring 3h and is mixed, the obtained reaction solution with complex compound;
(2) purification process: the reaction solution with complex compound is carried out purified treatment in without the box drainer of magnetic, and the processing time is 6h, the reaction solution after being purified; Precipitation reagent 25% sodium hydroxide solution is purified in without the box drainer of magnetic, the precipitation reagent after being purified;
(3) coprecipitation reaction: by reaction solution with the speed of 1.7L/h, precipitation reagent adds without in magnetic response still with the Rate Dispersion of 0.8L/h simultaneously, in the liquid phase environment having axial flow (350 turns per minute), radial flow (500 turns per minute) concurrently, control reaction temperature is 80 DEG C, regulate pH value 10.5 ~ 11.5, the reaction time is 20h; Make cobalt, magnesium 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 hydroxide of 19.2 μm, the slurry of inorganic salt mixt;
(4) removal of impurities process: this slurry removes inorganic salts, stabilizer in 95 DEG C of aqueous systems, obtained spherical cobalt magnesium hydroxide matrix;
(5) dry qualitative: this spherical cobalt magnesium hydroxide matrix is put into drying machine, 110 ± 5 DEG C, oxygen content is in the air of 18 ± 1%, 0.1Mpa pressure (gauge pressure), it is dry and qualitative that the reaction time is that 2.5h carries out anhydrating;
(6) reconstruction and optimization: by anhydrate dry and qualitative after spherical cobalt magnesium hydroxide matrix immigration calciner in be reconstructed optimization, reaction temperature is 630 ± 5 DEG C, 0.1Mpa pressure (gauge pressure), oxygen content be in the air of 18 ± 1% processing time be 17h, obtain tap density 2.9g/cm
3, average grain diameter 19 μm power lithium-ion battery positive electrode material precursor cobalt magnesium oxide (cobalt, magnesium mol ratio are 9.8:0.2).
Embodiment five: this lithium-ion-power cell preparation method of cobalt magnesium oxide, adopt coprecipitation preparation, concrete steps are as follows:
(1) complex compound is generated: in 3500ml water, add cobalt chloride 1195.4g and magnesium chloride 76.2g respectively, fully mix, and add 2.3g butanedioic acid C
4h
6o
4stabilizer carries out stirring 2.5h and mixes, the obtained reaction solution with complex compound;
(2) purification process: the reaction solution with complex compound is carried out purified treatment in without the box drainer of magnetic, and the processing time is 4h, the reaction solution after being purified; Precipitation reagent 25% sodium hydroxide solution is purified in without the box drainer of magnetic, the precipitation reagent after being purified;
(3) coprecipitation reaction: by reaction solution with the speed of 1.9L/h, precipitation reagent adds without in magnetic response still with the Rate Dispersion of 0.8L/h simultaneously, in the liquid phase environment having axial flow (360 turns per minute), radial flow (550 turns per minute) concurrently, control reaction temperature is 80 DEG C, regulate pH value 10 ~ 11, the reaction time is 16h; Make cobalt, magnesium 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 hydroxide of 18.8 μm, the slurry of inorganic salt mixt;
(4) removal of impurities process: this slurry removes inorganic salts, stabilizer in 90 DEG C of aqueous systems, obtained spherical cobalt magnesium hydroxide matrix;
(5) dry qualitative: this spherical cobalt magnesium hydroxide matrix is put into drying machine, 120 ± 5 DEG C, oxygen content is in the air of 18 ± 1%, 0.1Mpa pressure (gauge pressure), it is dry and qualitative that the reaction time is that 2h carries out anhydrating;
(6) reconstruction and optimization: by anhydrate dry and qualitative after spherical cobalt magnesium hydroxide matrix immigration calciner in be reconstructed optimization, reaction temperature is 620 ± 5 DEG C, 0.1Mpa pressure (gauge pressure), oxygen content be in the air of 18 ± 1% processing time be 18h, obtain tap density 2.9g/cm
3, average grain diameter 18.5 μm power lithium-ion battery positive electrode material precursor cobalt magnesium oxide (cobalt, magnesium mol ratio are 9.2:0.8).
Embodiment six: this lithium-ion-power cell preparation method of cobalt magnesium oxide, adopt coprecipitation preparation, concrete steps are as follows:
(1) complex compound is generated: in 4500ml water, add cobalt chloride 605.8g and magnesium chloride 1.34g respectively, fully mix, and add 2.5g citric acid C
6h
8o
7stabilizer carries out stirring 2.5h and mixes, the obtained reaction solution with complex compound;
(2) purification process: the reaction solution with complex compound is carried out purified treatment in without the box drainer of magnetic, and the processing time is 4h, the reaction solution after being purified; Precipitation reagent 25% sodium hydroxide solution is purified in without the box drainer of magnetic, the precipitation reagent after being purified;
(3) coprecipitation 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 axial flow (320 turns per minute), radial flow (520 turns per minute) concurrently, control reaction temperature is 80 DEG C, regulate pH value 10.5 ~ 11.5, the reaction time is 16h; Make cobalt, magnesium 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 hydroxide of 18.5 μm, the slurry of inorganic salt mixt;
(4) removal of impurities process: this slurry removes inorganic salts, stabilizer in 95 DEG C of aqueous systems, obtained spherical cobalt magnesium hydroxide matrix;
(5) dry qualitative: this spherical cobalt magnesium hydroxide matrix is put into drying machine, 110 ± 5 DEG C, oxygen content is in the air of 18 ± 1%, 0.1Mpa pressure (gauge pressure), it is dry and qualitative that the reaction time is that 2.5h carries out anhydrating;
(6) reconstruction and optimization: by anhydrate dry and qualitative after spherical cobalt magnesium hydroxide matrix immigration calciner in be reconstructed optimization, reaction temperature is 650 ± 5 DEG C, 0.1Mpa pressure (gauge pressure), oxygen content be in the air of 18 ± 1% processing time be 18h, obtain tap density 3.0g/cm
3, average grain diameter 18.3 μm power lithium-ion battery positive electrode material precursor cobalt magnesium oxide (cobalt, magnesium mol ratio are 9.95:0.05).
Embodiment seven: this lithium-ion-power cell preparation method of cobalt magnesium oxide, adopt coprecipitation preparation, concrete steps are as follows:
(1) complex compound is generated: in 3500ml water, add cobalt chloride 596.6g and magnesium chloride 5.34g respectively, fully mix, and add the citric acid C that 3.0g weight ratio is 2:1
6h
8o
7with butanedioic acid C
4h
6o
4stabilized with mixture agent is carried out stirring 3h and is mixed, the obtained reaction solution with complex compound;
(2) purification process: the reaction solution with complex compound is carried out purified treatment in without the box drainer of magnetic, and the processing time is 3h, the reaction solution after being purified; Precipitation reagent 25% sodium hydroxide solution is purified in without the box drainer of magnetic, the precipitation reagent after being purified;
(3) coprecipitation 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 axial flow (350 turns per minute), radial flow (540 turns per minute) concurrently, control reaction temperature is 75 DEG C, regulate pH value 10 ~ 11, the reaction time is 14h; Make cobalt, magnesium 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 hydroxide of 18.4 μm, the slurry of inorganic salt mixt;
(4) removal of impurities process: this slurry removes inorganic salts, stabilizer in 85 DEG C of aqueous systems, obtained spherical cobalt magnesium hydroxide matrix;
(5) dry qualitative: this spherical cobalt magnesium hydroxide matrix is put into drying machine, 120 ± 5 DEG C, oxygen content is in the air of 18 ± 1%, 0.1Mpa pressure (gauge pressure), it is dry and qualitative that the reaction time is that 2h carries out anhydrating;
(6) reconstruction and optimization: by anhydrate dry and qualitative after spherical cobalt magnesium hydroxide matrix immigration calciner in be reconstructed optimization, reaction temperature is 660 ± 5 DEG C, 0.1Mpa pressure (gauge pressure), oxygen content be in the air of 18 ± 1% processing time be 20h, obtain tap density 2.9g/cm
3, average grain diameter 18.1 μm power lithium-ion battery positive electrode material precursor cobalt magnesium oxide (cobalt, magnesium mol ratio are 9.8:0.2).
Embodiment eight: this lithium-ion-power cell preparation method of cobalt magnesium oxide, adopt coprecipitation preparation, concrete steps are as follows:
(1) complex compound is generated: in 6000ml water, add cobalt nitrate 2009g and magnesium nitrate 16.9g respectively, fully mix, and add the citric acid C that 4.5g weight ratio is 2:1
6h
8o
7with butanedioic acid C
4h
6o
4stabilized with mixture agent is carried out stirring 2.5h and is mixed, the obtained reaction solution with complex compound;
(2) purification process: the reaction solution with complex compound is carried out purified treatment in without the box drainer of magnetic, and the processing time is 6h, the reaction solution after being purified; Precipitation reagent 25% sodium hydroxide solution is purified in without the box drainer of magnetic, the precipitation reagent after being purified;
(3) coprecipitation reaction: by reaction solution with the speed of 2L/h, precipitation reagent adds without in magnetic response still with the Rate Dispersion of 0.9L/h simultaneously, in the liquid phase environment having axial flow (320 turns per minute), radial flow (520 turns per minute) concurrently, control reaction temperature is 75 DEG C, regulate pH value 10.5 ~ 11.5, the reaction time is 18h; Make cobalt, magnesium 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 hydroxide of 18 μm, the slurry of inorganic salt mixt;
(4) removal of impurities process: this slurry removes inorganic salts, stabilizer in 90 DEG C of aqueous systems, obtained spherical cobalt magnesium hydroxide matrix;
(5) dry qualitative: this spherical cobalt magnesium hydroxide matrix is put into drying machine, 110 ± 5 DEG C, oxygen content is in the air of 18 ± 1%, 0.1Mpa pressure (gauge pressure), it is dry and qualitative that the reaction time is that 2h carries out anhydrating;
(6) reconstruction and optimization: by anhydrate dry and qualitative after spherical cobalt magnesium hydroxide matrix immigration calciner in be reconstructed optimization, reaction temperature is 650 ± 5 DEG C, 0.1Mpa pressure (gauge pressure), oxygen content be in the air of 18 ± 1% processing time be 20h, obtain tap density 2.8g/cm
3, average grain diameter 17.8 μm power lithium-ion battery positive electrode material precursor cobalt magnesium oxide (cobalt, magnesium mol ratio are 9.9:0.1).
Embodiment nine: this lithium-ion-power cell preparation method of cobalt magnesium oxide, adopt coprecipitation preparation, concrete steps are as follows:
(1) complex compound is generated: in 5000ml water, add cobalt nitrate 900.9g and magnesium nitrate 12.5g respectively, fully mix, and add the citric acid C that 4.0g weight ratio is 2:1
6h
8o
7with butanedioic acid C
4h
6o
4stabilized with mixture agent is carried out stirring 2.5h and is mixed, the obtained reaction solution with complex compound;
(2) purification process: the reaction solution with complex compound is carried out purified treatment in without the box drainer of magnetic, and the processing time is 5h, the reaction solution after being purified; Precipitation reagent 25% sodium hydroxide solution is purified in without the box drainer of magnetic, the precipitation reagent after being purified;
(3) coprecipitation reaction: by reaction solution with the speed of 2L/h, precipitation reagent adds without in magnetic response still with the Rate Dispersion of 0.9L/h simultaneously, in the liquid phase environment having axial flow (400 turns per minute), radial flow (580 turns per minute) concurrently, control reaction temperature is 80 DEG C, regulate pH value 10.0 ~ 11.0, the reaction time is 16h; Make cobalt, magnesium 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 hydroxide of 19.1 μm, the slurry of inorganic salt mixt;
(4) removal of impurities process: this slurry removes inorganic salts, stabilizer in 95 DEG C of aqueous systems, obtained spherical cobalt magnesium hydroxide matrix;
(5) dry qualitative: this spherical cobalt magnesium hydroxide matrix is put into drying machine, 110 ± 5 DEG C, oxygen content is in the air of 18 ± 1%, 0.1Mpa pressure (gauge pressure), it is dry and qualitative that the reaction time is that 3h carries out anhydrating;
(6) reconstruction and optimization: by anhydrate dry and qualitative after spherical cobalt magnesium hydroxide matrix immigration calciner in be reconstructed optimization, reaction temperature is 620 ± 5 DEG C, 0.1Mpa pressure (gauge pressure), oxygen content be in the air of 18 ± 1% processing time be 22h, obtain tap density 3.0g/cm
3, average grain diameter 18.8 μm power lithium-ion battery positive electrode material precursor cobalt magnesium oxide (cobalt, magnesium mol ratio are 9.85:0.15).
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 (9)
1. a lithium-ion-power cell preparation method for cobalt magnesium oxide, is characterized in that, this lithium-ion-power cell cobalt magnesium oxide adopts coprecipitation preparation, and concrete steps are as follows:
(1) generate complex compound: get a certain proportion of cobalt salt and magnesium salts water-soluble, form the mixed aqueous solution of cobalt salt and magnesium salts; In described mixed aqueous solution, add stabilizer mix and stir and make it mix, obtain the reaction solution with complex compound;
(2) purification process: the precipitation reagent needed for the reaction solution with complex compound obtained in step (1) and reaction is put into carry out purified treatment without the box drainer 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, impurity such as removing inorganic salts, stabilizer etc., obtains class spherical cobalt magnesium hydroxide matrix;
(5) dry qualitative: institute's class that obtains spherical cobalt magnesium hydroxide matrix in step (4) to be carried out drying at a certain temperature in air atmosphere qualitative;
(6) reconstruction and optimization: institute's class that obtains spherical cobalt magnesium hydroxide matrix in step (5) is carried out high-temperature reconstruction optimization, thus obtains lithium-ion-power cell cobalt magnesium oxide.
2. the preparation method of lithium-ion-power cell cobalt magnesium oxide according to claim 1, is characterized in that, the described stabilizer in described step (1) is citric acid C
6h
8o
7or/and butanedioic acid C
4h
6o
4; 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.
3. the preparation method of lithium-ion-power cell cobalt magnesium oxide according to claim 1, it is characterized in that, cobalt ions in the described reaction solution that described step (1) is prepared and the total concentration of magnesium ion are 40 ~ 130g/l, and described cobalt salt and magnesium salts are 100:1 ~ 1.5 with the ratio of the total weight of described stabilizer.
4. the preparation method of cobalt magnesium oxide of the lithium-ion-power cell according to Claims 2 or 3, is characterized in that, cobalt salt described in described step (1) and magnesium salts and the mixed mixing time of described stabilizer are 1 ~ 3h.
5. the preparation method of lithium-ion-power cell cobalt magnesium 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 oxide according to claim 5, is characterized in that, in described step (2), the time of purification process is 2 ~ 6h.
7. the preparation method of lithium-ion-power cell cobalt magnesium 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 ~ 2L/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, radial flow is 300 ~ 400 turns/min, and axial flow is 500 ~ 600 turns/min; Regulate pH to be 9 ~ 12, reaction temperature is 70 ~ 85 DEG C, and the reaction time is 10 ~ 20h; Make cobalt ions and magnesium ion under the effect of stabilizer, co-precipitation equably, form slurry.
8. the preparation method of lithium-ion-power cell cobalt magnesium 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 oxide according to claim 7, it is characterized in that, in described step (5), spherical for described class cobalt magnesium hydroxide matrix is put into drying machine, temperature is set to 100 ~ 130 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, the preparation method of lithium-ion-power cell cobalt magnesium oxide according to claim 8, it is characterized in that, class spherical cobalt magnesium hydroxide matrix after qualitative to drying in described step (6) moves in calciner, it is 550 ~ 700 DEG C in reaction temperature, pressure is 0 ~ 0.02Mpa, oxygen volumn concentration is be reconstructed optimization in the air atmosphere of 15 ~ 20%, and the reaction time is 15 ~ 25h.
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