CN105322157A - Preparation method of manganese-doped lithium cobalt oxide of lithium polymer battery for charge pal - Google Patents
Preparation method of manganese-doped lithium cobalt oxide of lithium polymer battery for charge pal Download PDFInfo
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- CN105322157A CN105322157A CN201510728164.0A CN201510728164A CN105322157A CN 105322157 A CN105322157 A CN 105322157A CN 201510728164 A CN201510728164 A CN 201510728164A CN 105322157 A CN105322157 A CN 105322157A
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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
- H01M4/36—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
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
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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
- H01M4/139—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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- 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
- H01M4/36—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
- H01M4/50—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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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention relates to a preparation method of a manganese-doped lithium cobalt oxide of a lithium polymer battery for a charge pal. The method comprises the following steps: proportioning certain molar concentration of lithium salt and cobalt salt and a manganese salt at a certain ratio by a coprecipitation method; carrying out a chemical precipitation reaction on the mixture and a precipitant under the conditions of certain temperature, flow, pH value, stirring speed and the like and under a system with a mixture of a buffer agent, so as to form an atomic-scale homogeneous mixture of cobaltous hydroxide, lithium hydroxide and manganese hydroxide for precipitation; and carrying out a low-temperature dehydration and a high-temperature modification, so as to form the manganese-doped lithium cobalt oxide. A positive electrode of the prepared lithium polymer battery is excellent in electrical properties; a discharge platform is not easy to attenuate, and is resistant to heavy current charging and discharging and over-charging and over-discharging, and long in service lifetime. The lithium polymer battery is applicable to a high-capacity fast moving charge power supply.
Description
Technical field
The present invention relates to lithium polymer battery technical field, namely relate to a kind of charger baby lithium polymer battery preparation method of lithium and cobalt oxides mixing manganese.
Background technology
Along with the development of science and technology, increasing electronic product needs mobile RAPID CHARGING POWER SUPPLY, to meet people's needs demand of powering to electronic product whenever and wherever possible; People also more and more pay attention to the exploitation of the New Technologies of clean energy resource and energy storage material simultaneously.And current most mobile RAPID CHARGING POWER SUPPLY adopts is all lithium polymer battery, mainly because it has high-energy-density, high security, the superperformance such as renewable, arouse great concern.
The presoma preparing the positive electrode of lithium polymer battery is at present have chemical precipitation method according to the chemism of preparation mostly, 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, these technology mix in lithium polymer battery positive electrode material precursor in the application of the lithium and cobalt oxides preparation method of manganese that there are the following problems: (1) obtained material is because the dislocation of transition metal cobalt ions and lithium ion and Mn oxide are in charge and discharge process, crystal structure is unstable, lattice is easily out of shape, so that other atom, electronics, ion insertion and extraction is difficult or uneven, anti-over-charging discharge performance is poor, 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 lithium polymer battery preparation method of lithium and cobalt oxides and the product of preparation of mixing manganese.
Summary of the invention
The object of the invention is to, provide a kind of automaticity high, produce the controlled and preparation method mixing the lithium and cobalt oxides of manganese of the charger baby lithium polymer battery that automaticity is high clean, easy and simple to handle.
In order to solve the problems of the technologies described above, technical scheme of the present invention is: the preparation method mixing the lithium and cobalt oxides of manganese of this lithium polymer battery, and adopt coprecipitation preparation, concrete steps are as follows:
(1) central computer control controls to open the electric control valve of reaction solution conduit and the electric control valve of buffer agent solution, in dustfree environment downhill reaction container, add reaction solution and the buffer agent solution of cobalt salt, lithium salts and manganese salt, then close the electric control valve of solution conduit and the electric control valve of buffer agent solution;
(2) central computer control controls to start stirring motor, and mixing speed is 450 ~ 550r/min, slowly agitating solution, and mixing time is 2 ~ 3h;
(3) central computer control controls the electric control valve opening precipitant solution conduit, in the mixed solution in step (2), add precipitation reagent, and the speed that described precipitation reagent adds is 0.5 ~ 1L/h; During interpolation, mixing speed is that 100 ~ 200r/min, pH keep 9 ~ 12, after having added, closes the electric control valve of precipitant solution conduit;
(4) central computer control controls to start electric heater unit, and make the temperature in reaction vessel rise to 90 ~ 99 DEG C, carry out precipitation reaction, the reaction time is 9 ~ 12h, obtains slurry;
(5) central computer control controls the electric control valve opening reaction container bottom, the slurry obtained in step (4) is sent into knot screen, central computer control controls the electric control valve opening the deionized water conduit of knot screen, add and go dried up and the slurry in reaction vessel is embathed through repeatedly removal of impurities, when removal of impurities is embathed, temperature is 85 ~ 95 DEG C;
(6) central computer control controls the electric control valve opened bottom knot screen, rear material press-in filter is embathed in removal of impurities, through 300 object strainer filterings by pump;
(7) central computer control controls to open dryer electric control valve, transmission electric control valve and dryer oxygen and passes into valve, dryer temperature and oxygen intake are set, material after filtration is put into dryer, the temperature of dryer is set to 120 ~ 200 DEG C, pressure is less than or equal to 0.02Mpa, dry and heat setting under the air atmosphere condition of oxygen volumn concentration 15 ~ 20%, the reaction time is 1.5 ~ 3h, obtains the lithium polymer battery lithium and cobalt oxides mixing manganese.
Adopt technique scheme, the lithium salts of certain molar concentration and cobalt salt and manganese salt proportioning according to a certain percentage, in uniform temperature, flow, pH value, under the conditions such as mixing speed and under the system of mixture having a buffer, chemical precipitation reaction is carried out with precipitation reagent, thus formation cobalt hydroxide, lithium hydroxide, the atom level homogeneous mixture of manganous hydroxide and precipitating, then low temperature dewatering is passed through, high-temperature reconstruction, define the lithium and cobalt oxides mixing manganese, wherein during reaction solution by buffer and cobalt ions, manganese ion, lithium ion form respectively complex compound, there is certain stability, and control settling velocity like this, prevent the loose condition (of surface) of deposit seed, thus improve final prepared the lithium polymer battery apparent density of lithium and cobalt oxides and the tap density of mixing manganese, obtained lithium polymer battery with the lithium and cobalt oxides mixing manganese because each Elemental redistribution of cobalt lithium manganese is even, due to the embedding of manganese oxygen key, transition element and lithium ion inconsistent phenomenon in material are eliminated, the layer structure of lithium and cobalt oxides is more stable, the electrical property of the lithium polymer battery positive pole 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.In order to make buffer better and cobalt ions, manganese ion, lithium ion form complex state, usually stir 2 ~ 3h by after the aqueous solution of buffer and cobalt salt, lithium salts, manganese salt, guarantee that the cobalt salt in solution, lithium salts, manganese salt fully contact with buffer.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.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, the described buffer 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 lithium salts is that lithium chloride is or/and lithium nitrate; Described manganese salt is one or more mixing of cobalt chloride, manganese nitrate, manganese sulfate.All without containing amine groups in the buffer 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 total concentration of cobalt ions, lithium ion and manganese ion in the described reaction solution that described step (1) adds is 60 ~ 100g/l, and described cobalt salt, lithium salts and manganese salt are 1000:5 ~ 10 with the ratio of the total weight of described buffer.
Further improvement is, the described precipitation reagent in described step (3) is that NaOH is or/and potassium hydroxide.
Further improvement is, the electric heater unit of described step (4) is made up of two groups of heating rods, recorded the temperature of reaction vessel by temperature sensor, whether start with the wherein one group of heating rod controlling electric heater, maintain the temperature of reaction vessel in suitable temperature.
Further improvement is, in described step (3), pH value regulates is the pH value being recorded reaction vessel by pH value testing sensor; After, central computer control controls mixing speed to bring up to 500 ~ 600r/min, stirs 15 ~ 30min; Then stirring motor is closed.
Further improvement is, the concentration of the precipitation reagent in described step (3) is mass fraction is 20 ~ 30%.
Another technical problem that the present invention also will solve is, provides a kind of lattice, structure cell regular, the constitutionally stable lithium polymer battery lithium and cobalt oxides mixing manganese.
In order to solve the problems of the technologies described above, technical scheme of the present invention is: adopt above-mentioned lithium polymer battery with mix manganese lithium and cobalt oxides preparation method prepared by lithium polymer battery be Li by the molecular formula of the lithium and cobalt oxides mixing manganese
xco
ymn
zo
4, wherein: 0<X+Y+Z≤4, X > 0,0<X+Y<4,0<Z≤1.
This lithium polymer battery is applicable to the fast moving charge power supply of high power capacity.
Compared with prior art, the invention has the beneficial effects as follows: preparation method is simple, preparation process automation, be applicable to large-scale production, and preparation process 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 lithium manganese is even, the COD process of wastewater treatment process is simple; And without follow-up mixed processes, energy consumption is low, therefore do not produce environmentally harmful containing ammonia nitrogen substances; And embed manganese atom by stable between cobalt, lithium, oxygen atom, the lithium and cobalt oxides lattice mixing manganese of the lithium polymer battery obtained, structure cell are regular, Stability Analysis of Structures, is applicable to the positive electrode of the lithium polymer battery in charger baby and Large Copacity fast moving rechargeable battery.
Embodiment
embodiment one:this lithium polymer battery preparation method of lithium and cobalt oxides mixing manganese, adopt coprecipitation preparation, concrete steps are as follows:
Raw material is: cobalt chloride 240g, lithium chloride 1000g and manganese chloride 10g, and buffer is citric acid C
6h
8o
72g, cobalt chloride, lithium chloride and manganese chloride are dissolved in 13000ml deionized water, the reaction solution of obtained cobalt salt, lithium salts and manganese salt; Citric acid C
6h
8o
72g be dissolved in 30ml go dried up in obtained buffer agent solution; Precipitation reagent is NaOH, and mass fraction is 20%.
(1) central computer control controls to open the electric control valve of reaction solution conduit and the electric control valve of buffer agent solution, in dustfree environment downhill reaction container, add reaction solution and the buffer agent solution of cobalt salt, lithium salts and manganese salt, then close the electric control valve of solution conduit and the electric control valve of buffer agent solution;
(2) central computer control controls to start stirring motor, and mixing speed is 550r/min, slowly agitating solution, and mixing time is 2h;
(3) central computer control controls the electric control valve opening precipitant solution conduit, in the mixed solution in step (2), add precipitation reagent, and the speed that described precipitation reagent adds is 0.5L/h; During interpolation, mixing speed is that 100r/min, pH keep 9.5, and it is the pH value being recorded reaction vessel by pH value testing sensor that pH value regulates; After, central computer control controls mixing speed to bring up to 600r/min, stirs 15min; Then the electric control valve of stirring motor and closedown precipitant solution conduit is closed;
(4) central computer control controls to start electric heater unit, and make the temperature in reaction vessel rise to 90 DEG C, carry out precipitation reaction, the reaction time is 12h, obtains slurry;
(5) central computer control controls the electric control valve opening reaction container bottom, the slurry obtained in step (4) is sent into knot screen, central computer control controls the electric control valve opening the deionized water conduit of knot screen, add and go dried up and the slurry in reaction vessel is embathed through repeatedly removal of impurities, when removal of impurities is embathed, temperature is 85 DEG C;
(6) central computer control controls the electric control valve opened bottom knot screen, rear material press-in filter is embathed in removal of impurities, through 300 object strainer filterings by pump;
(7) central computer control controls to open dryer electric control valve and dryer oxygen passes into valve, dryer temperature and oxygen intake are set, material after filtration is put into dryer, the temperature of dryer is set to 150 DEG C, pressure is 0.02Mpa, dry and heat setting under the air atmosphere condition of oxygen volumn concentration 15%, reaction time is 3h, obtain the lithium polymer battery lithium and cobalt oxides mixing manganese, its average grain diameter is 12 μm, for lighium polymer ion battery positive electrode material precursor.
embodiment two:
This lithium polymer battery preparation method of lithium and cobalt oxides mixing manganese, adopt coprecipitation preparation, concrete steps are as follows:
Raw material is: lithium chloride 600g, cobalt chloride 192g and manganese chloride 8g, and buffer is citric acid C
6h
8o
73g, cobalt chloride, lithium chloride and manganese chloride are dissolved in 10000ml deionized water, the reaction solution of obtained cobalt salt, lithium salts and manganese salt; Citric acid C
6h
8o
7be dissolved in 30ml go dried up in obtained buffer agent solution; Precipitation reagent is NaOH, and mass fraction is 25%.
(1) central computer control controls to open the electric control valve of reaction solution conduit and the electric control valve of buffer agent solution, in dustfree environment downhill reaction container, add reaction solution and the buffer agent solution of cobalt salt, lithium salts and manganese salt, then close the electric control valve of solution conduit and the electric control valve of buffer agent solution;
(2) central computer control controls to start stirring motor, and mixing speed is 500r/min, slowly agitating solution, and mixing time is 2.5h;
(3) central computer control controls the electric control valve opening precipitant solution conduit, in the mixed solution in step (2), add precipitation reagent, and the speed that described precipitation reagent adds is 0.8L/h; During interpolation, mixing speed is that 150r/min, pH keep 9.8, and it is the pH value being recorded reaction vessel by pH value testing sensor that pH value regulates; After, central computer control controls mixing speed to bring up to 550r/min, stirs 23min; Then the electric control valve of stirring motor and closedown precipitant solution conduit is closed;
(4) central computer control controls to start electric heater unit, and make the temperature in reaction vessel rise to 95 DEG C, carry out precipitation reaction, the reaction time is 9h, obtains slurry;
(5) central computer control controls the electric control valve opening reaction container bottom, the slurry obtained in step (4) is sent into knot screen, central computer control controls the electric control valve opening the deionized water conduit of knot screen, add and go dried up and the slurry in reaction vessel is embathed through repeatedly removal of impurities, when removal of impurities is embathed, temperature is 90 DEG C;
(6) central computer control controls the electric control valve opened bottom knot screen, rear material press-in filter is embathed in removal of impurities, through 300 object strainer filterings by pump;
(7) central computer control controls to open dryer electric control valve and dryer oxygen passes into valve, dryer temperature and oxygen intake are set, material after filtration is put into dryer, the temperature of dryer is set to 180 DEG C, pressure is 0.01Mpa, dry and heat setting under the air atmosphere condition of oxygen volumn concentration 15%, reaction time is 2.5h, obtain the lithium polymer battery lithium and cobalt oxides mixing manganese, its average grain diameter is 12.5 μm, for lighium polymer ion battery positive electrode material precursor.
embodiment three:
This lithium polymer battery preparation method of lithium and cobalt oxides mixing manganese, adopt coprecipitation preparation, concrete steps are as follows:
Raw material is: lithium chloride 491g, cobalt chloride 103g and manganese chloride 6g, and buffer is citric acid C
6h
8o
71.5g, cobalt chloride, lithium chloride and manganese chloride are dissolved in 10000ml deionized water, the reaction solution of obtained cobalt salt, lithium salts and manganese salt; Citric acid C
6h
8o
7be dissolved in 30ml go dried up in obtained buffer agent solution; Precipitation reagent is NaOH, and mass fraction is 30%.
(1) central computer control controls to open the electric control valve of reaction solution conduit and the electric control valve of buffer agent solution, in dustfree environment downhill reaction container, add reaction solution and the buffer agent solution of cobalt salt, lithium salts and manganese salt, then close the electric control valve of solution conduit and the electric control valve of buffer agent solution;
(2) central computer control controls to start stirring motor, and mixing speed is 450r/min, slowly agitating solution, and mixing time is 3h;
(3) central computer control controls the electric control valve opening precipitant solution conduit, in the mixed solution in step (2), add precipitation reagent, and the speed that described precipitation reagent adds is 1L/h; During interpolation, mixing speed is that 200r/min, pH keep 10, and it is the pH value being recorded reaction vessel by pH value testing sensor that pH value regulates; After, central computer control controls mixing speed to bring up to 500r/min, stirs 30min; Then the electric control valve of stirring motor and closedown precipitant solution conduit is closed;
(4) central computer control controls to start electric heater unit, and make the temperature in reaction vessel rise to 98 DEG C, carry out precipitation reaction, the reaction time is 10h, obtains slurry;
(5) central computer control controls the electric control valve opening reaction container bottom, the slurry obtained in step (4) is sent into knot screen, central computer control controls the electric control valve opening the deionized water conduit of knot screen, add and go dried up and the slurry in reaction vessel is embathed through repeatedly removal of impurities, when removal of impurities is embathed, temperature is 95 DEG C;
(6) central computer control controls the electric control valve opened bottom knot screen, rear material press-in filter is embathed in removal of impurities, through 300 object strainer filterings by pump;
(7) central computer control controls to open dryer electric control valve and dryer oxygen passes into valve, dryer temperature and oxygen intake are set, material after filtration is put into dryer, the temperature of dryer is set to 200 DEG C, pressure is 0.02Mpa, dry and heat setting under the air atmosphere condition of oxygen volumn concentration 20%, reaction time is 2h, obtain the lithium polymer battery lithium and cobalt oxides mixing manganese, its average grain diameter is 11.5 μm, for lighium polymer ion battery positive electrode material precursor.
embodiment four:
This lithium polymer battery preparation method of lithium and cobalt oxides mixing manganese, adopt coprecipitation preparation, concrete steps are as follows:
Raw material is: lithium nitrate 600g, cobalt nitrate 192g and manganese nitrate 8g, and buffer is 2 ethyl hexanoic acid 3g, and cobalt nitrate, lithium nitrate and manganese nitrate are dissolved in 10000ml deionized water, the reaction solution of obtained cobalt salt, lithium salts and manganese salt; 2 ethyl hexanoic acid be dissolved in 30ml go dried up in obtained buffer agent solution; Precipitation reagent is NaOH, and mass fraction is 25%.
(1) central computer control controls to open the electric control valve of reaction solution conduit and the electric control valve of buffer agent solution, in dustfree environment downhill reaction container, add reaction solution and the buffer agent solution of cobalt salt, lithium salts and manganese salt, then close the electric control valve of solution conduit and the electric control valve of buffer agent solution;
(2) central computer control controls to start stirring motor, and mixing speed is 500r/min, slowly agitating solution, and mixing time is 2.5h;
(3) central computer control controls the electric control valve opening precipitant solution conduit, in the mixed solution in step (2), add precipitation reagent, and the speed that described precipitation reagent adds is 0.8L/h; During interpolation, mixing speed is that 150r/min, pH keep 9.8, and it is the pH value being recorded reaction vessel by pH value testing sensor that pH value regulates; After, central computer control controls mixing speed to bring up to 550r/min, stirs 23min; Then the electric control valve of stirring motor and closedown precipitant solution conduit is closed;
(4) central computer control controls to start electric heater unit, and make the temperature in reaction vessel rise to 95 DEG C, carry out precipitation reaction, the reaction time is 9h, obtains slurry;
(5) central computer control controls the electric control valve opening reaction container bottom, the slurry obtained in step (4) is sent into knot screen, central computer control controls the electric control valve opening the deionized water conduit of knot screen, add and go dried up and the slurry in reaction vessel is embathed through repeatedly removal of impurities, when removal of impurities is embathed, temperature is 90 DEG C;
(6) central computer control controls the electric control valve opened bottom knot screen, rear material press-in filter is embathed in removal of impurities, through 300 object strainer filterings by pump;
(7) central computer control controls to open dryer electric control valve and dryer oxygen passes into valve, dryer temperature and oxygen intake are set, material after filtration is put into dryer, the temperature of dryer is set to 180 DEG C, pressure is 0.02Mpa, dry and heat setting under the air atmosphere condition of oxygen volumn concentration 15%, reaction time is 2.5h, obtain the lithium polymer battery lithium and cobalt oxides mixing manganese, its average grain diameter is 12.2 μm, for lighium polymer ion battery positive electrode material precursor.
embodiment five:
This lithium polymer battery preparation method of lithium and cobalt oxides mixing manganese, adopt coprecipitation preparation, concrete steps are as follows:
Raw material is: lithium nitrate 600g, cobalt nitrate 192g and manganese sulfate 8g, and buffer is 2 ethyl hexanoic acid 3g, and cobalt nitrate, lithium nitrate and manganese sulfate are dissolved in 10000ml deionized water, the reaction solution of obtained cobalt salt, lithium salts and manganese salt; 2 ethyl hexanoic acid be dissolved in 30ml go dried up in obtained buffer agent solution; Precipitation reagent is NaOH, and mass fraction is 25%.
(1) central computer control controls to open the electric control valve of reaction solution conduit and the electric control valve of buffer agent solution, in dustfree environment downhill reaction container, add reaction solution and the buffer agent solution of cobalt salt, lithium salts and manganese salt, then close the electric control valve of solution conduit and the electric control valve of buffer agent solution;
(2) central computer control controls to start stirring motor, and mixing speed is 500r/min, slowly agitating solution, and mixing time is 2.5h;
(3) central computer control controls the electric control valve opening precipitant solution conduit, in the mixed solution in step (2), add precipitation reagent, and the speed that described precipitation reagent adds is 0.8L/h; During interpolation, mixing speed is that 150r/min, pH keep 9.8, and it is the pH value being recorded reaction vessel by pH value testing sensor that pH value regulates; After, central computer control controls mixing speed to bring up to 580r/min, stirs 20min; Then the electric control valve of stirring motor and closedown precipitant solution conduit is closed;
(4) central computer control controls to start electric heater unit, and make the temperature in reaction vessel rise to 95 DEG C, carry out precipitation reaction, the reaction time is 10h, obtains slurry;
(5) central computer control controls the electric control valve opening reaction container bottom, the slurry obtained in step (4) is sent into knot screen, central computer control controls the electric control valve opening the deionized water conduit of knot screen, add and go dried up and the slurry in reaction vessel is embathed through repeatedly removal of impurities, when removal of impurities is embathed, temperature is 90 DEG C;
(6) central computer control controls the electric control valve opened bottom knot screen, rear material press-in filter is embathed in removal of impurities, through 300 object strainer filterings by pump;
(7) central computer control controls to open dryer electric control valve and dryer oxygen passes into valve, dryer temperature and oxygen intake are set, material after filtration is put into dryer, the temperature of dryer is set to 160 DEG C, pressure is 0.02Mpa, dry and heat setting under the air atmosphere condition of oxygen volumn concentration 15%, reaction time is 2.5h, obtain the lithium polymer battery lithium and cobalt oxides mixing manganese, its average grain diameter is 12.3 μm, for lighium polymer ion battery positive electrode material precursor.
Above-described specific embodiment; object of the present invention, technical scheme and beneficial effect are further described; be understood that; the foregoing is only specific embodiments of the invention; be not limited to the present invention; within the spirit and principles in the present invention all, any amendment made, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (9)
1. the preparation method mixing the lithium and cobalt oxides of manganese of charger baby lithium polymer battery, is characterized in that, this lithium polymer battery lithium and cobalt oxides mixing manganese adopts coprecipitation preparation, and concrete steps are as follows:
(1) central computer control controls to open the electric control valve of reaction solution conduit and the electric control valve of buffer agent solution, in dustfree environment downhill reaction container, add reaction solution and the buffer agent solution of cobalt salt, lithium salts and manganese salt, then close the electric control valve of solution conduit and the electric control valve of buffer agent solution;
(2) central computer control controls to start stirring motor, and mixing speed is 450 ~ 550r/min, slowly agitating solution, and mixing time is 2 ~ 3h;
(3) central computer control controls the electric control valve opening precipitant solution conduit, in the mixed solution in step (2), add precipitation reagent, and the speed that described precipitation reagent adds is 0.5 ~ 1L/h; During interpolation, mixing speed is that 100 ~ 200r/min, pH keep 9 ~ 12, after having added, closes the electric control valve of precipitant solution conduit;
(4) central computer control controls to start electric heater unit, and make the temperature in reaction vessel rise to 90 ~ 99 DEG C, carry out precipitation reaction, the reaction time is 9 ~ 12h, obtains slurry;
(5) central computer control controls the electric control valve opening reaction container bottom, the slurry obtained in step (4) is sent into knot screen, central computer control controls the electric control valve opening the deionized water conduit of knot screen, add and go dried up and the slurry in reaction vessel is embathed through repeatedly removal of impurities, when removal of impurities is embathed, temperature is 85 ~ 95 DEG C;
(6) central computer control controls the electric control valve opened bottom knot screen, rear material press-in filter is embathed in removal of impurities, through 300 object strainer filterings by pump;
(7) central computer control controls to open dryer electric control valve, transmission electric control valve and dryer oxygen and passes into valve, dryer temperature and oxygen intake are set, material after filtration is put into dryer, the temperature of dryer is set to 120 ~ 200 DEG C, pressure is less than or equal to 0.02Mpa, dry and heat setting under the air atmosphere condition of oxygen volumn concentration 15 ~ 20%, the reaction time is 1.5 ~ 3h, obtains the lithium polymer battery lithium and cobalt oxides mixing manganese.
2. the lithium polymer battery according to claim 1 preparation method of lithium and cobalt oxides mixing manganese, is characterized in that, the described cobalt salt in described step (1) is one or more mixing of cobalt chloride, cobalt nitrate, cobaltous sulfate; Described lithium salts is that lithium chloride is or/and lithium nitrate; Described manganese salt is one or more mixing of cobalt chloride, manganese nitrate, manganese sulfate; Described buffer is citric acid C
6h
8o
7or/and 2 ethyl hexanoic acid.
3. the lithium polymer battery according to claim 2 preparation method of lithium and cobalt oxides mixing manganese, it is characterized in that, the total concentration of cobalt ions, lithium ion and manganese ion in the described reaction solution that described step (1) adds is 60 ~ 100g/l, and described cobalt salt, lithium salts and manganese salt are 1000:5 ~ 10 with the ratio of the total weight of described buffer.
4. the lithium polymer battery according to claim 1 preparation method of lithium and cobalt oxides mixing manganese, it is characterized in that, the described precipitation reagent in described step (3) is that NaOH is or/and potassium hydroxide.
5. the preparation method of lithium and cobalt oxides mixing manganese of the lithium polymer battery according to claim 3 or 4, it is characterized in that, the electric heater unit of described step (4) is made up of two groups of heating rods, the temperature of reaction vessel is recorded by temperature sensor, whether start with the wherein one group of heating rod controlling electric heater, maintain the temperature of reaction vessel in suitable temperature.
6. the lithium polymer battery according to claim 4 preparation method of lithium and cobalt oxides mixing manganese, is characterized in that, in described step (3), pH value regulates is the pH value being recorded reaction vessel by pH value testing sensor; After, central computer control controls mixing speed to bring up to 500 ~ 600r/min, stirs 15 ~ 30min; Then stirring motor is closed.
7. the lithium polymer battery according to claim 4 preparation method of lithium and cobalt oxides mixing manganese, it is characterized in that, the concentration of the precipitation reagent in described step (3) is mass fraction is 20 ~ 30%.
8. one kind adopt lithium polymer battery as described in any one of claim 1-7 with mix manganese lithium and cobalt oxides preparation method prepared by the lithium polymer battery lithium and cobalt oxides mixing manganese, it is characterized in that, the lithium polymer battery of acquisition is Li by the molecular formula of the lithium and cobalt oxides mixing manganese
xco
ymn
zo
4, wherein: 0<X+Y+Z≤4, X > 0,0<X+Y<4,0<Z≤1.
9. the lithium polymer battery according to claim 8 preparation method of lithium and cobalt oxides mixing manganese, it is characterized in that, this lithium polymer battery is applicable to the fast moving charge power supply of high power capacity.
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