CN103746110A - Preparation method of nickel-cobalt-manganese ternary material and anode material for lithium ion battery - Google Patents
Preparation method of nickel-cobalt-manganese ternary material and anode material for lithium ion battery Download PDFInfo
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- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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- H01M4/52—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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- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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Abstract
The invention provides a preparation method of a nickel-cobalt-manganese ternary material; under the stirring effect, the co-precipitation reaction is implemented for soluble salt of nickel, soluble salt of cobalt, soluble salt of manganese and precipitating agent under the condition of 7.5-8.5 of pH value to obtain a nickel-cobalt-manganese ternary material precursor; the stirring speed is 600-1000 r/m; the reaction temperature of the co-precipitation reaction is 40-60 DEG C; the lithiation is implemented for the nickel-cobalt-manganese ternary material precursor to obtain the nickel-cobalt-manganese ternary material. The preparation method prepares the nickel-cobalt-manganese ternary material precursor with spherical morphology through comprehensively controlling the stirring speed and reaction temperature of the co-precipitation reaction and the pH value of the reaction system in the reaction process in the process of preparing the nickel-cobalt-manganese ternary material precursor; the method for preparing the nickel-cobalt-manganese ternary material, provided by the invention, is environment-friendly, and has lower cost.
Description
Technical field
The present invention relates to technical field of lithium ion, relate in particular to a kind of preparation method of nickel-cobalt-manganese ternary material.
Background technology
Lithium battery (Lithium Cell) refers to the electrochemical system of basic electrochemistry unit that contains lithium (comprising lithium metal, lithium alloy, lithium ion and lighium polymer).Lithium battery can be divided into two classes: lithium metal battery and lithium ion battery.Lithium ion battery does not contain the lithium of metallic state, and preparation technology is simple, and can charge, and has wide application.
The positive electrode of lithium ion battery is generally the salt compounds that comprises nickel-cobalt-manganese ternary element, can be divided into the positive electrode of stratiform pattern and the positive electrode of spherical morphology, the anode material for lithium-ion batteries of spherical morphology not only tap density is high, but also thering is excellent mobility, dispersiveness and processing characteristics, the lithium ion battery preparing has higher volume energy density.Therefore, the anode material for lithium-ion batteries of preparation spherical morphology is the important directions of research lithium ion battery.
At present, the technique of the anode material for lithium-ion batteries of preparation spherical morphology is, first prepare the nickel Co-Mn compound of spherical morphology as the presoma of anode material for lithium-ion batteries, after again the presoma of the anode material for lithium-ion batteries obtaining being mixed with lithium source, heat-treat, can obtain anode material for lithium-ion batteries, the presoma of preparing the anode material for lithium-ion batteries of spherical morphology is the key that obtains high performance lithium ion battery anode material.Application number is the preparation method that 201210356523.0 Chinese patent discloses a kind of nickel-cobalt-manganese ternary material, detailed process is, the consumption that is 1:1:4 according to mol ratio takes nickelous sulfate, cobaltous sulfate and manganese sulfate, above-mentioned nickelous sulfate, cobaltous sulfate and manganese sulfate are mixed with polyethylene glycol, and being mixed with nickel cobalt manganese, to mix molar concentration be the solution A that the molar concentration of 0.5mol/L, polyethylene glycol is 0.05mol/L; With deionized water, sodium carbonate and complexing agent being mixed with to concentration of sodium carbonate is the solution B that 1mol/L, complexing agent concentration are 0.5mol/L, and described complexing agent is that mass ratio is the sodium tartrate of 2:1 and the mixture of sulfosalicylic acid sodium salt; Controlling the temperature of reaction system is 1 ℃, and solution A and solution B stream are joined in reaction vessel, and controlling pH value is 7.0, reacts 2h, by the product ageing 6h obtaining; Product after ageing is filtered, by after the filter cake deionized water washing after filtering 4 times, at 80 ℃, dry 24h, obtain spherical carbonate presoma; The ratio that is 1:0.58 with lithium carbonate according to mass ratio by described carbonate precursor mixes, and under the oxidizing atmosphere of 650 ℃, sintering 24 hours, obtains nickel-cobalt-manganese ternary material.
Although prior art can prepare the nickel-cobalt-manganese ternary material of the spherical morphology that tap density is higher, but this method of preparing spherical morphology nickel-cobalt-manganese ternary material is used complexing agent or surfactant, use complexing agent or surfactant can increase the difficulty of final wash, cost of sewage disposal is high, and causes serious problem of environmental pollution.
Summary of the invention
In view of this, the object of the present invention is to provide a kind of preparation method of nickel-cobalt-manganese ternary material, preparation method's environmental protection of nickel-cobalt-manganese ternary material provided by the invention, cost are lower.
The preparation method who the invention provides a kind of nickel-cobalt-manganese ternary material, comprises the following steps:
1), under stirring action, under the condition that is 7.5～8.5 in pH value by the soluble-salt of the soluble-salt of the soluble-salt of nickel, cobalt, manganese and precipitation reagent, carry out coprecipitation reaction, obtain nickel-cobalt-manganese ternary material presoma, the speed of described stirring is 600 revs/min～1000 revs/min, and the reaction temperature of described coprecipitation reaction is 40 ℃～60 ℃;
2), described nickel-cobalt-manganese ternary material presoma is calcined, obtain intermediate product;
3), described intermediate product is mixed with lithium source after sintering, obtain nickel-cobalt-manganese ternary material.
Preferably, the speed of described stirring is 700 revs/min～900 revs/min.
Preferably, described pH value is 8.0～8.5.
Preferably, the reaction temperature of described coprecipitation reaction is 45 ℃～55 ℃.
Preferably, the reaction time of described coprecipitation reaction is 6h～12h.
Preferably, the ratio of the molal quantity of the total molal quantity of the soluble-salt of the soluble-salt of described nickel, cobalt and the soluble-salt of manganese and precipitation reagent is 1:(1～2).
Preferably, described precipitation reagent is one or more in carbonate.
Preferably, described precipitation reagent is precipitant solution, and the molar concentration of described precipitant solution is 1.0mol/L～2.5mol/L.
Preferably, the soluble-salt of described nickel comprises one or more in the halide of nickelous sulfate, nickel nitrate and nickel;
The soluble-salt of described cobalt comprises one or more in the halide of cobaltous sulfate, cobalt nitrate and cobalt;
The soluble-salt of described manganese comprises one or more in the halide of manganese sulfate, manganese nitrate and manganese.
The invention provides a kind of anode material for lithium-ion batteries, nickel-cobalt-manganese ternary material prepared by method described in technique scheme is as anode material for lithium-ion batteries.
The invention provides a kind of preparation method of nickel-cobalt-manganese ternary material, 1), under stirring action comprise the following steps:, under the condition that is 7.5～8.5 in pH value by the soluble-salt of the soluble-salt of the soluble-salt of nickel, cobalt, manganese and precipitation reagent, carry out coprecipitation reaction, obtain nickel-cobalt-manganese ternary material presoma, the speed of described stirring is 600 revs/min～1000 revs/min, and the reaction temperature of described coprecipitation reaction is 40 ℃～60 ℃; 2), described nickel-cobalt-manganese ternary material presoma is calcined, obtain intermediate product; 3), described intermediate product is mixed with lithium source after sintering, obtain nickel-cobalt-manganese ternary material.The present invention prepares the mixing speed of coprecipitation reaction in nickel-cobalt-manganese ternary material presoma process by Comprehensive Control, the pH value technological parameter of reaction system in reaction temperature and course of reaction, and then forming core speed and the speed of growth of crystal in coprecipitation reaction process have been controlled, make to reach balance between crystal forming core and growth, thereby prepare the nickel-cobalt-manganese ternary material presoma of spherical morphology, the narrow diameter distribution of this nickel-cobalt-manganese ternary material presoma, this nickel-cobalt-manganese ternary material presoma is carried out to lithiumation and can obtain nickel-cobalt-manganese ternary material, the tap density of nickel-cobalt-manganese ternary material prepared by the present invention is high.Nickel-cobalt-manganese ternary material prepared by the present invention can be used as anode material for lithium-ion batteries and uses.Compared with prior art, the present invention is without using complexing agent or surfactant to prepare the nickel-cobalt-manganese ternary material of spherical morphology, and therefore method environmental protection, the cost of preparing nickel-cobalt-manganese ternary material provided by the invention is lower.In addition, preparation method's technique of nickel-cobalt-manganese ternary material provided by the invention is simple, easy and simple to handle.
Accompanying drawing explanation
Fig. 1 is the ESEM picture of the nickel-cobalt-manganese ternary material presoma that obtains of the embodiment of the present invention 1;
Fig. 2 is the electrochemical property test result of the anode material for lithium-ion batteries that obtains of the embodiment of the present invention 1;
Fig. 3 is the ESEM picture of the nickel-cobalt-manganese ternary material presoma that obtains of the embodiment of the present invention 2;
Fig. 4 is the ESEM picture of the nickel-cobalt-manganese ternary material presoma that obtains of the embodiment of the present invention 3;
Fig. 5 is the ESEM picture of the nickel-cobalt-manganese ternary material presoma that obtains of the embodiment of the present invention 4;
Fig. 6 is the particle diameter distribution map of the nickel-cobalt-manganese ternary material presoma that obtains of the embodiment of the present invention 6.
Embodiment
The preparation method who the invention provides a kind of nickel-cobalt-manganese ternary material, comprises the following steps:
1), under stirring action, under the condition that is 7.5～8.5 in pH value by the soluble-salt of the soluble-salt of the soluble-salt of nickel, cobalt, manganese and precipitation reagent, carry out coprecipitation reaction, obtain nickel-cobalt-manganese ternary material presoma, the speed of described stirring is 600 revs/min～1000 revs/min, and the reaction temperature of described coprecipitation reaction is 40 ℃～60 ℃;
2), described nickel-cobalt-manganese ternary material presoma is calcined, obtain intermediate product;
3), described intermediate product is mixed with lithium source after sintering, obtain nickel-cobalt-manganese ternary material.
The present invention prepares the mixing speed of coprecipitation reaction in nickel-cobalt-manganese ternary material presoma process by Comprehensive Control, the pH value technological parameter of reaction system in reaction temperature and course of reaction, and then forming core speed and the speed of growth of crystal in coprecipitation reaction process have been controlled, make to reach balance between crystal forming core and growth, thereby prepare the nickel-cobalt-manganese ternary material presoma of spherical morphology, the narrow diameter distribution of this nickel-cobalt-manganese ternary material presoma, this nickel-cobalt-manganese ternary material presoma is carried out to lithiumation and can obtain nickel-cobalt-manganese ternary material, the tap density of nickel-cobalt-manganese ternary material prepared by the present invention is high.Nickel-cobalt-manganese ternary material prepared by the present invention can be used as anode material for lithium-ion batteries and uses.Compared with prior art, the present invention is without using complexing agent or surfactant to prepare the nickel-cobalt-manganese ternary material of spherical morphology, and therefore method environmental protection, the cost of preparing nickel-cobalt-manganese ternary material provided by the invention is lower.In addition, preparation method's technique of nickel-cobalt-manganese ternary material provided by the invention is simple, easy and simple to handle.
The present invention, under stirring action, carries out coprecipitation reaction under the condition that is 7.5～8.5 by the soluble-salt of the soluble-salt of the soluble-salt of nickel, cobalt, manganese and precipitation reagent in pH value, obtains nickel-cobalt-manganese ternary material presoma; The speed of described stirring is 600 revs/min～1000 revs/min; The reaction temperature of described coprecipitation reaction is 40 ℃～60 ℃.In the present invention, the speed of described stirring is preferably 700 revs/min～900 revs/min, more preferably 750 revs/min～850 revs/min, most preferably is 800 revs/min.
In the present invention, the soluble-salt of described nickel preferably includes one or more in the halide of nickelous sulfate, nickel nitrate and nickel; The more preferably one in nickelous sulfate, nickel nitrate and nickel chloride.In the present invention, the soluble-salt of described cobalt preferably includes one or more in the halide of cobaltous sulfate, cobalt nitrate and cobalt; The more preferably one in cobaltous sulfate, cobalt nitrate and cobalt chloride.In the present invention, the soluble-salt of described manganese preferably includes one or more in the halide of manganese sulfate, manganese nitrate and manganese; The more preferably one in manganese sulfate, manganese nitrate and manganese chloride.The source of soluble-salt, the soluble-salt of cobalt and the soluble-salt of manganese of the present invention to described nickel does not have special restriction, adopts soluble-salt, the soluble-salt of cobalt and the soluble-salt of manganese of the nickel of mentioned kind well known to those skilled in the art; As bought and obtain by market.
In the present invention, the mol ratio of the manganese in the cobalt in the nickel in the soluble-salt of described nickel, the soluble-salt of cobalt and the soluble-salt of manganese is preferably (1-a-b): a:b, 0<a<1,0≤b<1,0<a+b<1.
In the present invention, described precipitation reagent is preferably one or more in carbonate, more preferably sodium carbonate.In the present invention, described precipitation reagent is preferably precipitant solution, and the molar concentration of described precipitant solution is preferably 1.0mol/L～2.5mol/L, more preferably 1.5mol/L～2mol/L.
In the present invention, described pH value is preferably 8.0～8.4.The present invention can be by controlling the soluble-salt of described nickel, the soluble-salt of cobalt, soluble-salt and the precipitation reagent consumption control pH value of manganese.In the present invention, the ratio of the molal quantity that the soluble-salt of the soluble-salt of described nickel, the soluble-salt of cobalt and manganese is total and the molal quantity of precipitation reagent is preferably 1:(1～2), more preferably 1:1.
In the present invention, the reaction temperature of described coprecipitation reaction is preferably 45 ℃～55 ℃, more preferably 48 ℃～52 ℃.In the present invention, the reaction time of described coprecipitation reaction is preferably 6h～12h, more preferably 8h～10h.
The present invention is preferably under above-mentioned stirring action, under the condition that is 7.5～8.5 in pH value by the mixed solution of the soluble-salt of the soluble-salt of the soluble-salt of nickel, cobalt and manganese and above-mentioned precipitation reagent, carry out above-mentioned coprecipitation reaction, obtain nickel-cobalt-manganese ternary material presoma.The preparation method of the mixed solution of soluble-salt, the soluble-salt of cobalt and the soluble-salt of manganese of the present invention to described nickel does not have special restriction, adopts the technical scheme of preparing mixed solution well known to those skilled in the art.In the present invention, consumption, the Kind and source of the soluble-salt of the soluble-salt of described nickel, the soluble-salt of cobalt and manganese are consistent with consumption, the Kind and source of soluble-salt, the soluble-salt of cobalt and the soluble-salt of manganese of the nickel described in technique scheme, do not repeat them here.In the present invention, in the mixed solution of the soluble-salt of the soluble-salt of described nickel, the soluble-salt of cobalt and manganese, nickel ion, cobalt ions and the total molar concentration of manganese ion are preferably 1.0mol/L～2.5mol/L, more preferably 1.5mol/L～2mol/L.
In order better to control the pH value in above-mentioned coprecipitation reaction process, the present invention preferably provides sodium carbonate liquor as reaction end liquid, under above-mentioned stirring action, liquid at the bottom of the soluble-salt of the soluble-salt of the soluble-salt of above-mentioned nickel, cobalt, manganese, precipitation reagent and reaction is mixed, carry out above-mentioned coprecipitation reaction, obtain nickel-cobalt-manganese ternary material presoma, at the bottom of described reaction, the pH value of liquid is preferably 7.5～8.5; More preferably under above-mentioned stirring action, the soluble-salt of the soluble-salt of the soluble-salt of above-mentioned nickel, cobalt, manganese and precipitation reagent stream are joined in reaction end liquid and carries out above-mentioned coprecipitation reaction, obtain nickel-cobalt-manganese ternary material presoma.
In the present invention, the pH value of liquid more preferably 8.0～8.4 at the bottom of described reaction.The present invention preferably regulates the pH value of liquid at the bottom of described reaction with acid solution, make the pH value of liquid at the bottom of described reaction in 7.5～8.5 scope.In the present invention, described acid solution is preferably one or more in sulfuric acid solution, hydrochloric acid solution, acetum and salpeter solution, more preferably the one in sulfuric acid solution, hydrochloric acid solution, acetum and salpeter solution.In the present invention, the molar concentration of described acid solution is preferably 0.5mol/L～2.5mol/L, more preferably 1.8mol/L～2.2mol/L.In the present invention, at the bottom of described reaction, the molar concentration of liquid is preferably 0.05mol/L～0.2mol/L, more preferably 0.1mol/L～0.15mol/L.
The present invention does not have special restriction to the equipment of described coprecipitation reaction, and in an embodiment of the present invention, described coprecipitation reaction can carry out in reactor.The present invention is preferably under above-mentioned stirring action, liquid at the bottom of above-mentioned reaction is heated after joining reactor, again the soluble-salt of the soluble-salt of the soluble-salt of above-mentioned nickel, cobalt, manganese and precipitation reagent stream are joined in described reactor and carries out above-mentioned coprecipitation reaction, obtain nickel-cobalt-manganese ternary material presoma.In the present invention, at the bottom of described reaction, the filling rate of liquid is preferably 15%～25%.In the present invention, the soluble-salt of described nickel, the solubility of cobalt, the soluble-salt of manganese and the charging rate of precipitation reagent are preferably 5mL/h～1.5L/h, more preferably 0.8L/h～1.2L/h independently of one another.In the present invention, the temperature of described heating is consistent with the reaction temperature of the coprecipitation reaction described in technique scheme, does not repeat them here.
After described coprecipitation reaction completes, the present invention preferably carries out ageing by the reaction solution obtaining, and obtains product; By dry after described product washing, obtain nickel-cobalt-manganese ternary material presoma.In the present invention, the pH value of the temperature of described ageing and reaction solution is consistent with the reaction temperature of coprecipitation reaction described in technique scheme and pH value, does not repeat them here.In the present invention, the time of described ageing is preferably 3h～6h, more preferably 4h～5h.
Obtain after product, the present invention preferably, by dry after described product washing, obtains nickel-cobalt-manganese ternary material presoma.The present invention does not have special restriction to the method for described washing, adopts washing technology scheme well known to those skilled in the art; In the present invention, the reagent of described washing is preferably water, more preferably deionized water.The present invention does not have special restriction to described dry method, adopts dry technology scheme well known to those skilled in the art.In the present invention, described dry temperature is preferably 80 ℃～120 ℃, more preferably 90 ℃～110 ℃; The described dry time is preferably 10 hours～and 14 hours.
The nickel-cobalt-manganese ternary material presoma that the present invention prepares has the molecular formula shown in formula (I):
(Mn
1-a-bNi
aCo
b)CO
3?（I）；
In formula (I), 0<a<1,0≤b<1,0<a+b<1.
Obtain after nickel-cobalt-manganese ternary material presoma, the present invention calcines described nickel-cobalt-manganese ternary material presoma, obtains intermediate product.In the present invention, the time of described calcining is preferably 12h～24h, more preferably 14h～20h; The temperature of described calcining is preferably 450 ℃～550 ℃, more preferably 470 ℃～530 ℃.
Obtain after intermediate product, the present invention carries out sintering after described intermediate product is mixed with lithium source, obtains anode material for lithium-ion batteries.In the present invention, the transition metal in described nickel-cobalt-manganese ternary material presoma and the mol ratio of the lithium in lithium source are preferably (1-x): (1+x), and 0≤x≤0.2.The present invention does not have special restriction to the method for described mixing, adopts hybrid technology scheme well known to those skilled in the art, and described intermediate product and lithium source are mixed.In the present invention, described lithium source is preferably one or both in lithium carbonate and lithium hydroxide, more preferably the one in lithium carbonate and lithium hydroxide.The present invention does not have special restriction to the source in described lithium source, adopts the lithium source of mentioned kind well known to those skilled in the art, as bought and be obtained by market.
In the present invention, the temperature of described sintering is preferably 800 ℃～900 ℃, more preferably 820 ℃～880 ℃; The time of described sintering is preferably 6h～24h, and more preferably 8h～20h, most preferably is 10h～18h.The present invention does not have special restriction to the equipment of described sintering, adopts agglomerating plant well known to those skilled in the art; Concrete, in an embodiment of the present invention, the equipment of described sintering can be Muffle furnace (Muffle furnace); In other embodiment, described agglomerating plant can also be tube furnace.
The nickel-cobalt-manganese ternary material that the present invention prepares has the molecular formula shown in formula (II):
Li
1+x(Mn
1-a-bNi
aCo
b)
1-xO
2?（II）
In formula (II), 0≤x≤0.2,0<a<1,0≤b<1,0<a+b<1.
The invention provides a kind of anode material for lithium-ion batteries, nickel-cobalt-manganese ternary material prepared by method described in technique scheme is as anode material for lithium-ion batteries.The nickel-cobalt-manganese ternary material that described in technique scheme prepared by method can be used as anode material for lithium-ion batteries and uses, and this lithium ion anode material has good chemical property.
The present invention carries out elementary analysis test to the nickel-cobalt-manganese ternary material presoma preparing, and test result is that the molecular formula of the nickel-cobalt-manganese ternary material presoma prepared of the present invention is consistent with formula (I).The present invention carries out scanning electron microscope analysis test to the nickel-cobalt-manganese ternary material presoma preparing, test result shows, the pattern of the nickel-cobalt-manganese ternary material presoma that the present invention obtains is spherical morphology, and the particle diameter narrow distribution of nickel-cobalt-manganese ternary material presoma.The present invention carries out elementary analysis test to the nickel-cobalt-manganese ternary material preparing, and test result is that the molecular formula of the nickel-cobalt-manganese ternary material that the present invention obtains is consistent with formula (II).The tap density of the nickel-cobalt-manganese ternary material that the present invention adopts tap density tester to test to prepare, test result is that the tap density of the nickel-cobalt-manganese ternary material that the present invention obtains is 2.25g/cm
3～2.5g/cm
3, tap density is higher.
The nickel-cobalt-manganese ternary material that the present invention is obtained is as anode material for lithium-ion batteries, the chemical property of test anode material for lithium-ion batteries, test result is, anode material for lithium-ion batteries is discharged and recharged with the speed of 20mA/g, its capacity discharging and recharging can reach 180mAh/g～280mAh/g, discharge and recharge 50 times～100 times cyclical stabilities good, anode material for lithium-ion batteries provided by the invention has good chemical property.
The invention provides a kind of preparation method of nickel-cobalt-manganese ternary material, 1), under stirring action comprise the following steps:, under the condition that is 7.5～8.5 in pH value by the soluble-salt of the soluble-salt of the soluble-salt of nickel, cobalt, manganese and precipitation reagent, carry out coprecipitation reaction, obtain nickel-cobalt-manganese ternary material presoma, the speed of described stirring is 600 revs/min～1000 revs/min, and the reaction temperature of described coprecipitation reaction is 40 ℃～60 ℃; 2), described nickel-cobalt-manganese ternary material presoma is calcined, obtain intermediate product; 3), described intermediate product is mixed with lithium source after sintering, obtain nickel-cobalt-manganese ternary material.The present invention prepares the mixing speed of coprecipitation reaction in nickel-cobalt-manganese ternary material presoma process by Comprehensive Control, the pH value technological parameter of reaction system in reaction temperature and course of reaction, and then forming core speed and the speed of growth of crystal in coprecipitation reaction process have been controlled, make to reach balance between crystal forming core and growth, thereby prepare the nickel-cobalt-manganese ternary material presoma of spherical morphology, the narrow diameter distribution of this nickel-cobalt-manganese ternary material presoma, this nickel-cobalt-manganese ternary material presoma is carried out to lithiumation and can obtain nickel-cobalt-manganese ternary material, the tap density of nickel-cobalt-manganese ternary material prepared by the present invention is high.Nickel-cobalt-manganese ternary material prepared by the present invention can be used as anode material for lithium-ion batteries and uses.Compared with prior art, the present invention is without using complexing agent or surfactant to prepare the nickel-cobalt-manganese ternary material of spherical morphology, and therefore method environmental protection, the cost of preparing nickel-cobalt-manganese ternary material provided by the invention is lower.In addition, preparation method's technique of nickel-cobalt-manganese ternary material provided by the invention is simple, easy and simple to handle.
In order to further illustrate the present invention, preparation method and anode material for lithium-ion batteries below in conjunction with embodiment to nickel-cobalt-manganese ternary material provided by the invention are described in detail, but they can not be interpreted as to limiting the scope of the present invention.
Embodiment 1
Manganese sulfate, nickelous sulfate and cobaltous sulfate are dissolved in water, obtain the mixed solution of manganese sulfate, nickelous sulfate and cobaltous sulfate; The mol ratio of described manganese sulfate, nickelous sulfate and cobaltous sulfate is 0.7:0.2:0.1, and in the mixed solution of described manganese sulfate, nickelous sulfate and cobaltous sulfate, the total molar concentration of manganese ion, nickel ion and cobalt ions is 2.0mol/L;
The aqueous sodium carbonate that preparation molar concentration is 2.1mol/L is as precipitation reagent;
The preparation molar concentration aqueous sodium carbonate that is 0.15mol/L, then regulates its pH value with the acetum that molar concentration is 2.0mol/L, and the aqueous sodium carbonate that obtain pH value and be 8.3, molar concentration is 0.15mol/L is as reacting end liquid;
Liquid at the bottom of above-mentioned reaction is placed in to reactor, and at the bottom of described reaction, the volume of liquid is reactor volume 20%, and described reactor volume is 10.0L.By liquid low whipping speed at the bottom of described reaction, be to be heated to 50 ℃ under the condition of 600 revs/min, the mixed solution of above-mentioned manganese sulfate, nickelous sulfate and cobaltous sulfate and precipitation reagent stream are joined and in described reactor, carries out coprecipitation reaction, the mixed solution of described manganese sulfate, nickelous sulfate and cobaltous sulfate and the charging rate of precipitation reagent are 1.0L/h, feed time is 8h, and the pH value of controlling described coprecipitation reaction is 8.0～8.4.
After above-mentioned coprecipitation reaction finishes, ageing 4h under the condition that is 8.0～8.4 at 50 ℃, pH value by the reaction solution obtaining, obtains product; Described product, with being dried 10 hours after deionized water washing at 100 ℃, is obtained to nickel-cobalt-manganese ternary material presoma.
Above-mentioned nickel-cobalt-manganese ternary material presoma is carried out to the calcining of 12 hours at 500 ℃, obtain intermediate product;
After the above-mentioned intermediate product that is 1:0.7061 by mass ratio mixes with lithium carbonate, in Muffle furnace, at 800 ℃, carry out the sintering of 24 hours, obtain nickel-cobalt-manganese ternary material.
The nickel-cobalt-manganese ternary material presoma that the embodiment of the present invention 1 is obtained carries out elementary analysis test, and test result is that the molecular formula of the nickel-cobalt-manganese ternary material presoma that the embodiment of the present invention 1 obtains is (Mn
0.7ni
0.2co
0.1) CO
3.The nickel-cobalt-manganese ternary material presoma that the embodiment of the present invention 1 is obtained carries out sem test, and as shown in Figure 1, Fig. 1 is the ESEM picture of the nickel-cobalt-manganese ternary material presoma that obtains of the embodiment of the present invention 1 to test result.As seen from Figure 1, the nickel-cobalt-manganese ternary material presoma that the embodiment of the present invention 1 obtains is spherical morphology, and its average grain diameter is 13.0 μ m.
The nickel-cobalt-manganese ternary material that the embodiment of the present invention 1 is obtained carries out elementary analysis test, and test result is that the molecular formula of the nickel-cobalt-manganese ternary material that obtains of the embodiment of the present invention 1 is Li
1.2(Mn
0.7ni
0.2co
0.1)
0.8o
2.The tap density of the nickel-cobalt-manganese ternary material that the employing tap density tester test embodiment of the present invention 1 obtains, test result is that the tap density of the nickel-cobalt-manganese ternary material that the embodiment of the present invention 1 obtains is 2.4g/cm
3, tap density is higher.
The nickel-cobalt-manganese ternary material that the embodiment of the present invention 1 is obtained is as anode material for lithium-ion batteries, according to the method described in technique scheme, test its chemical property, as shown in Figure 2, Fig. 2 is the electrochemical property test result of the anode material for lithium-ion batteries that obtains of the embodiment of the present invention 1 to test result.As shown in Figure 2, the anode material for lithium-ion batteries that the embodiment of the present invention 1 is obtained discharges and recharges with the speed of 20mA/g, its capacity discharging and recharging can reach 260mAh/g, discharge and recharge 100 cyclical stabilities good, the anode material for lithium-ion batteries that the embodiment of the present invention 1 obtains has good chemical property.
Embodiment 2
Manganese nitrate, nickel nitrate and cobalt nitrate are dissolved in water, obtain the mixed solution of manganese nitrate, nickel nitrate and cobalt nitrate; The mol ratio of described manganese nitrate, nickel nitrate and cobalt nitrate is 0.65:0.15:0.2, and in the mixed solution of described manganese nitrate, nickel nitrate and cobalt nitrate, the total molar concentration of manganese ion, nickel ion and cobalt ions is 2.0mol/L;
The aqueous sodium carbonate that preparation molar concentration is 2.2mol/L is as precipitation reagent;
The preparation molar concentration aqueous sodium carbonate that is 0.15mol/L, then regulates its pH value with the salpeter solution that molar concentration is 0.5mol/L, and the aqueous sodium carbonate that obtain pH value and be 8.3, molar concentration is 0.15mol/L is as reacting end liquid;
Liquid at the bottom of above-mentioned reaction is placed in to reactor, and at the bottom of described reaction, the volume of liquid is reactor volume 20%, and described reactor volume is 2.0L.By liquid low whipping speed at the bottom of described reaction, be to be heated to 60 ℃ under the condition of 1000 revs/min, the mixed solution of above-mentioned manganese nitrate, nickel nitrate and cobalt nitrate and precipitation reagent stream are joined and in described reactor, carries out coprecipitation reaction, the mixed solution of described manganese nitrate, nickel nitrate and cobalt nitrate and the charging rate of precipitation reagent are 5mL/h, feed time is 6h, and the pH value of controlling described coprecipitation reaction is 8.0～8.4.
After described coprecipitation reaction finishes, ageing 3h under the condition that is 8.0～8.4 at 60 ℃, pH value by the reaction solution obtaining, obtains product; Described product, with being dried 14 hours after deionized water washing at 80 ℃, is obtained to nickel-cobalt-manganese ternary material presoma.
Described nickel-cobalt-manganese ternary material presoma is carried out to the calcining of 16 hours at 500 ℃, obtain intermediate product;
After the above-mentioned intermediate product that is 1:0.0811 by mass ratio mixes with lithium hydroxide, in Muffle furnace, at 850 ℃, carry out the sintering of 12 hours, obtain nickel-cobalt-manganese ternary material.
The nickel-cobalt-manganese ternary material presoma that the embodiment of the present invention 2 is obtained carries out elementary analysis test, and test result is that the molecular formula of the nickel-cobalt-manganese ternary material that obtains of the embodiment of the present invention 2 is (Mn
0.65ni
0.15co
0.2) CO
3.The nickel-cobalt-manganese ternary material presoma that the embodiment of the present invention 2 is obtained carries out sem test, and as shown in Figure 3, Fig. 3 is the ESEM picture of the nickel-cobalt-manganese ternary material presoma that obtains of the embodiment of the present invention 2 to test result.As seen from Figure 3, the nickel-cobalt-manganese ternary material that the embodiment of the present invention 2 obtains is spherical morphology, and its average grain diameter is 14.0 μ m.
The nickel-cobalt-manganese ternary material that the embodiment of the present invention 2 is obtained carries out elementary analysis test, and test result is that the molecular formula of the nickel-cobalt-manganese ternary material that obtains of the embodiment of the present invention 2 is Li
1.2(Mn
0.65ni
0.15co
0.2)
0.8o
2.The tap density of the nickel-cobalt-manganese ternary material obtaining according to the method test embodiment of the present invention 2 described in embodiment 1, test result is that the tap density of the nickel-cobalt-manganese ternary material that the embodiment of the present invention 2 obtains is 2.45g/cm
3, tap density is high.
The nickel-cobalt-manganese ternary material that the embodiment of the present invention 2 is obtained is as anode material for lithium-ion batteries, the chemical property of the anode material of lithium battery obtaining according to the method test embodiment of the present invention 2 described in technique scheme, test result is, the anode material of lithium battery that the embodiment of the present invention 2 is obtained discharges and recharges with the speed of 20mA/g, its capacity discharging and recharging can reach 275mAh/g, discharge and recharge 50 cyclical stabilities good, the anode material of lithium battery that the embodiment of the present invention 2 obtains has good chemical property.
Embodiment 3
Manganese chloride, nickel chloride and cobalt chloride are dissolved in water, obtain the mixed solution of manganese chloride, nickel chloride and cobalt chloride; The mol ratio of described manganese chloride, nickel chloride and cobalt chloride is 0.4:0.4:0.2, and in the mixed solution of described manganese chloride, nickel chloride and cobalt chloride, the total molar concentration of nickel ion, cobalt ions and manganese ion is 2.0mol/L;
The aqueous sodium carbonate that preparation molar concentration is 2.2mol/L is as precipitation reagent;
The preparation molar concentration aqueous sodium carbonate that is 0.15mol/L, then regulates its pH value with the hydrochloric acid solution that molar concentration is 0.5mol/L, and the aqueous sodium carbonate that obtain pH value and be 8.3, molar concentration is 0.15mol/L is as reacting end liquid;
Liquid at the bottom of described reaction is placed in to reactor, and at the bottom of described reaction, the volume of liquid is reactor volume 25%, and described reactor volume is 10.0L.By liquid low whipping speed at the bottom of described reaction, be to be heated to 60 ℃ under the condition of 700 revs/min, the mixed solution of above-mentioned manganese chloride, nickel chloride and cobalt chloride and precipitation reagent stream are joined and in described reactor, carries out coprecipitation reaction, the mixed solution of described manganese chloride, nickel chloride and cobalt chloride and the charging rate of precipitation reagent are 1.0L/h, feed time is 8h, and the pH value of controlling described coprecipitation reaction is 8.0～8.4.
After described coprecipitation reaction finishes, by the reaction solution obtaining, at 60 ℃, pH value, be ageing 6h under 8.0～8.4 conditions, obtain product; Described product, with being dried 11 hours after deionized water washing at 120 ℃, is obtained to nickel-cobalt-manganese ternary material presoma.
Described nickel-cobalt-manganese ternary material presoma is carried out to the calcining of 12 hours at 550 ℃, obtain intermediate product;
After the above-mentioned intermediate product that is 1:0.4735 by mass ratio mixes with lithium carbonate, in Muffle furnace, at 900 ℃, carry out the sintering of 6 hours, obtain nickel-cobalt-manganese ternary material.
The nickel-cobalt-manganese ternary material presoma that the embodiment of the present invention 3 is obtained carries out elementary analysis test, and test result is that the molecular formula of the nickel-cobalt-manganese ternary material presoma that obtains of the embodiment of the present invention 3 is (Mn
0.4ni
0.4co
0.2) CO
3.The nickel-cobalt-manganese ternary material presoma that the embodiment of the present invention 3 is obtained carries out sem test, and as shown in Figure 4, Fig. 4 is the ESEM picture of the nickel-cobalt-manganese ternary material presoma that obtains of the embodiment of the present invention 3 to test result.As seen from Figure 4, the nickel-cobalt-manganese ternary material that the embodiment of the present invention 3 obtains is spherical morphology, and its average grain diameter is 10.0 μ m.
The nickel-cobalt-manganese ternary material that the embodiment of the present invention 3 is obtained carries out elementary analysis test, and test result is that the molecular formula of the nickel-cobalt-manganese ternary material that obtains of the embodiment of the present invention 3 is LiMn
0.4ni
0.4co
0.2o
2.The tap density of the nickel-cobalt-manganese ternary material obtaining according to the method test embodiment of the present invention 3 described in embodiment 1, test result is that the tap density of the nickel-cobalt-manganese ternary material that the embodiment of the present invention 3 obtains is 2.3g/cm
3, tap density is high.
The nickel-cobalt-manganese ternary material that the embodiment of the present invention 3 is obtained is as anode material for lithium-ion batteries, the chemical property of the anode material of lithium battery obtaining according to the method test embodiment of the present invention 3 described in technique scheme, test result is, the anode material of lithium battery that the embodiment of the present invention 3 is obtained discharges and recharges with the speed of 20mA/g, its capacity discharging and recharging can reach 180mAh/g, discharge and recharge 50 cyclical stabilities good, the anode material of lithium battery that the embodiment of the present invention 3 obtains has good chemical property.
Embodiment 4
Manganese chloride, nickel chloride and cobalt nitrate are dissolved in water, obtain the mixed solution of manganese chloride, nickel chloride and cobalt nitrate; The mol ratio of described manganese chloride, nickel chloride and cobalt nitrate is 1:1:1, and in the mixed solution of described manganese chloride, nickel chloride and cobalt nitrate, the total molar concentration of nickel ion, cobalt ions and manganese ion is 2.0mol/L;
The aqueous sodium carbonate that preparation molar concentration is 2.2mol/L is as precipitation reagent;
The preparation molar concentration aqueous sodium carbonate that is 0.1mol/L, then regulates its pH value with the acetum that molar concentration is 2.0mol/L, and the aqueous sodium carbonate that obtain pH value and be 8.3, molar concentration is 0.1mol/L is as reacting end liquid;
Liquid at the bottom of above-mentioned reaction is placed in to reactor, and at the bottom of described reaction, the volume of liquid is reactor volume 20%, and described reactor volume is 10.0L.By liquid low whipping speed at the bottom of described reaction, be to be heated to 60 ℃ under the condition of 800 revs/min, the mixed solution of above-mentioned manganese chloride, nickel chloride and cobalt nitrate and precipitation reagent stream are joined and in described reactor, carries out coprecipitation reaction, the mixed solution of described manganese chloride, nickel chloride and cobalt nitrate and the charging rate of precipitation reagent are 1L/h, feed time is 8h, and the pH value of controlling described coprecipitation reaction is 8.0～8.4.
After described coprecipitation reaction finishes, ageing 4h under the condition that is 8.0～8.4 at 60 ℃, pH value by the reaction solution obtaining, obtains product; Described product, with being dried 12 hours after deionized water washing at 100 ℃, is obtained to nickel-cobalt-manganese ternary material presoma.
Described nickel-cobalt-manganese ternary material presoma is carried out to the calcining of 12 hours at 550 ℃, obtain intermediate product;
After the above-mentioned intermediate product that is 1:0.4685 by mass ratio mixes with lithium carbonate, in Muffle furnace, at 900 ℃, carry out the sintering of 6 hours, obtain nickel-cobalt-manganese ternary material.
The nickel-cobalt-manganese ternary material presoma that the embodiment of the present invention 4 is obtained carries out elementary analysis test, and test result is that the molecular formula of the nickel-cobalt-manganese ternary material presoma that obtains of the embodiment of the present invention 4 is (Mn
1/3ni
1/3co
1/3) CO
3.The nickel-cobalt-manganese ternary material presoma that the embodiment of the present invention 4 is obtained carries out sem test, and as shown in Figure 5, Fig. 5 is the ESEM picture of the nickel-cobalt-manganese ternary material that obtains of the embodiment of the present invention 4 to test result.As seen from Figure 5, the nickel-cobalt-manganese ternary material that the embodiment of the present invention 4 obtains is spherical morphology, and its average grain diameter is 9.0 μ m.
The nickel-cobalt-manganese ternary material that the embodiment of the present invention 4 is obtained carries out elementary analysis test, and test result is that the molecular formula of the nickel-cobalt-manganese ternary material that obtains of the embodiment of the present invention 4 is LiMn
1/3ni
1/3co
1/3o
2.The tap density of the nickel-cobalt-manganese ternary material obtaining according to the method test embodiment of the present invention 4 described in embodiment 1, test result is that the tap density of the nickel-cobalt-manganese ternary material that the embodiment of the present invention 4 obtains is 2.25g/cm
3, tap density is high.
The nickel-cobalt-manganese ternary material that the embodiment of the present invention 4 is obtained is as anode material for lithium-ion batteries, the chemical property of the anode material of lithium battery obtaining according to the method test embodiment of the present invention 4 described in technique scheme, test result is, the anode material of lithium battery that the embodiment of the present invention 4 is obtained discharges and recharges with the speed of 20mA/g, its capacity discharging and recharging can reach 185mAh/g, discharge and recharge 100 cyclical stabilities good, the anode material of lithium battery that the embodiment of the present invention 4 obtains has good chemical property.
Embodiment 5
Manganese sulfate, nickelous sulfate and cobaltous sulfate are dissolved in water, obtain the mixed solution of manganese sulfate, nickelous sulfate and cobaltous sulfate; The mol ratio of described manganese sulfate, nickelous sulfate and cobaltous sulfate is 0.65:0.15:0.2, and in the mixed solution of described manganese sulfate, nickelous sulfate and cobaltous sulfate, the total molar concentration of nickel ion, cobalt ions and manganese ion is 1.0mol/L;
The aqueous sodium carbonate that preparation molar concentration is 1.0mol/L is as precipitation reagent;
The preparation molar concentration aqueous sodium carbonate that is 0.05mol/L, then regulates its pH value with the acetum that molar concentration is 2.0mol/L, and the aqueous sodium carbonate that obtain pH value and be 7.5, molar concentration is 0.05mol/L is as reacting end liquid;
Liquid at the bottom of described reaction is placed in to reactor, and at the bottom of described reaction, the volume of liquid is reactor volume 20%, and described reactor volume is 10.0L.By liquid low whipping speed at the bottom of described reaction, be to be heated to 40 ℃ under the condition of 700 revs/min, the mixed solution of above-mentioned manganese sulfate, nickelous sulfate and cobaltous sulfate and precipitation reagent stream are joined and in described reactor, carries out coprecipitation reaction, the mixed solution of described manganese sulfate, nickelous sulfate and cobaltous sulfate and precipitation reagent charging rate are 1L/h, feed time is 7h, and the pH value of controlling described coprecipitation reaction is 7.5～8.0.
After described coprecipitation reaction finishes, ageing 4h under the condition that is 7.5～8.0 at 40 ℃, pH value by the reaction solution obtaining, obtains product; Described product, with being dried 13 hours after deionized water washing at 100 ℃, is obtained to nickel-cobalt-manganese ternary material presoma.
Described nickel-cobalt-manganese ternary material presoma is carried out to the calcining of 12 hours at 450 ℃, obtain intermediate product;
After the above-mentioned intermediate product that is 1:0.701 by mass ratio mixes with lithium carbonate, in Muffle furnace, at 800 ℃, carry out the sintering of 24 hours, obtain nickel-cobalt-manganese ternary material.
The nickel-cobalt-manganese ternary material presoma that the embodiment of the present invention 5 is obtained carries out elementary analysis test, and test result is that the molecular formula of the nickel-cobalt-manganese ternary material presoma that obtains of the embodiment of the present invention 5 is (Mn
0.65ni
0.15co
0.2) CO
3.The nickel-cobalt-manganese ternary material presoma that the embodiment of the present invention 5 is obtained carries out sem test, and test result is, the nickel-cobalt-manganese ternary material that the embodiment of the present invention 5 obtains is spherical morphology, and its average grain diameter is 13.5 μ m.
The nickel-cobalt-manganese ternary material that the embodiment of the present invention 5 is obtained carries out elementary analysis test, and test result is that the molecular formula of the nickel-cobalt-manganese ternary material that obtains of the embodiment of the present invention 5 is Li
1.2(Mn
0.7ni
0.2co
0.1)
0.8o
2.The tap density of the nickel-cobalt-manganese ternary material obtaining according to the method test embodiment of the present invention 5 described in embodiment 1, test result is that the tap density of the nickel-cobalt-manganese ternary material that the embodiment of the present invention 5 obtains is 2.5g/cm
3, tap density is high.
The nickel-cobalt-manganese ternary material that the embodiment of the present invention 5 is obtained is as anode material for lithium-ion batteries, the chemical property of the anode material of lithium battery obtaining according to the method test embodiment of the present invention 5 described in technique scheme, test result is, the anode material of lithium battery that the embodiment of the present invention 5 is obtained discharges and recharges with the speed of 20mA/g, its capacity discharging and recharging can reach 280mAh/g, discharge and recharge 80 cyclical stabilities good, the anode material of lithium battery that the embodiment of the present invention 5 obtains has good chemical property.
Embodiment 6
Manganese sulfate, nickelous sulfate and cobaltous sulfate are dissolved in water, obtain the mixed solution of manganese sulfate, nickelous sulfate and cobaltous sulfate; The mol ratio of described manganese sulfate, nickelous sulfate and cobaltous sulfate is 0.675:0.175:0.15, and in the mixed solution of described manganese sulfate, nickelous sulfate and cobaltous sulfate, the total molar concentration of nickel ion, cobalt ions and manganese ion is 2.5mol/L;
The aqueous sodium carbonate that preparation molar concentration is 2.5mol/L is as precipitation reagent;
The preparation molar concentration aqueous sodium carbonate that is 0.2mol/L, then regulates its pH value with the acetum that molar concentration is 2.5mol/L, and the aqueous sodium carbonate that obtain pH value and be 8.5, molar concentration is 0.2mol/L is as reacting end liquid;
Liquid at the bottom of above-mentioned reaction is placed in to reactor, and at the bottom of described reaction, the volume of liquid is reactor volume 20%, and described reactor volume is 2.0L.By liquid low whipping speed at the bottom of described reaction, be to be heated to 50 ℃ under the condition of 1000 revs/min, the mixed solution of above-mentioned manganese sulfate, nickelous sulfate and cobaltous sulfate and precipitation reagent stream are joined and in described reactor, carries out coprecipitation reaction, the mixed solution of described manganese sulfate, nickelous sulfate and cobaltous sulfate and precipitation reagent charging rate are 5.0mL/h, feed time is 10h, and the pH value of controlling described coprecipitation reaction is 8.3～8.5.
After described coprecipitation reaction finishes, ageing 4h under the condition that is 8.3～8.5 at 50 ℃, pH value by the reaction solution obtaining, obtains product; Described product, with being dried 12 hours after deionized water washing at 100 ℃, is obtained to nickel-cobalt-manganese ternary material presoma.
Described nickel-cobalt-manganese ternary material presoma is carried out to the calcining of 18 hours at 500 ℃, obtain intermediate product;
By mass ratio, be the sintering carrying out at 850 ℃ in Muffle furnace after the above-mentioned intermediate product of 1:0.7033 mixes with lithium carbonate 16 hours, obtain nickel-cobalt-manganese ternary material.
The nickel-cobalt-manganese ternary material presoma that the embodiment of the present invention 6 is obtained carries out elementary analysis test, and test result is that the molecular formula of the nickel-cobalt-manganese ternary material presoma that obtains of the embodiment of the present invention 6 is (Mn
0.675ni
0.175co
0.15) CO
3.The nickel-cobalt-manganese ternary material presoma that the embodiment of the present invention 6 is obtained carries out sem test, test result is, the nickel-cobalt-manganese ternary material presoma that the embodiment of the present invention 6 obtains is spherical morphology, its average grain diameter is 13.5 μ m, the particle diameter of the nickel-cobalt-manganese ternary material presoma that the sem test result of the nickel-cobalt-manganese ternary material presoma obtaining according to the embodiment of the present invention 6 is prepared embodiment 6 is analyzed, analysis result as shown in Figure 6, Fig. 6 is the particle diameter distribution map of the nickel-cobalt-manganese ternary material presoma that obtains of the embodiment of the present invention 6, as shown in Figure 6, the particle diameter narrow distribution of the nickel-cobalt-manganese ternary material presoma that the embodiment of the present invention 6 obtains.
The nickel-cobalt-manganese ternary material that the embodiment of the present invention 6 is obtained carries out elementary analysis test, and test result is that the molecular formula of the nickel-cobalt-manganese ternary material that obtains of the embodiment of the present invention 6 is Li
1.2(Mn
0.675ni
0.175co
0.15)
0.8o
2.The tap density of the nickel-cobalt-manganese ternary material obtaining according to the method test embodiment of the present invention 6 described in embodiment 1, test result is that the tap density of the nickel-cobalt-manganese ternary material that the embodiment of the present invention 6 obtains is 2.4g/cm
3, tap density is high.
The nickel-cobalt-manganese ternary material that the embodiment of the present invention 6 is obtained is as anode material for lithium-ion batteries, the chemical property of the anode material of lithium battery obtaining according to the method test embodiment of the present invention 6 described in technique scheme, test result is, the anode material of lithium battery that the embodiment of the present invention 6 is obtained discharges and recharges with the speed of 20mA/g, its capacity discharging and recharging can reach 280mAh/g, discharge and recharge 100 cyclical stabilities good, the anode material of lithium battery that the embodiment of the present invention 6 obtains has good chemical property.
The invention provides a kind of preparation method of nickel-cobalt-manganese ternary material, 1), under stirring action comprise the following steps:, under the condition that is 7.5～8.5 in pH value by the soluble-salt of the soluble-salt of the soluble-salt of nickel, cobalt, manganese and precipitation reagent, carry out coprecipitation reaction, obtain nickel-cobalt-manganese ternary material presoma, the speed of described stirring is 600 revs/min～1000 revs/min, and the reaction temperature of described coprecipitation reaction is 40 ℃～60 ℃; 2), described nickel-cobalt-manganese ternary material presoma is calcined, obtain intermediate product; 3), described intermediate product is mixed with lithium source after sintering, obtain nickel-cobalt-manganese ternary material.The present invention prepares the mixing speed of coprecipitation reaction in nickel-cobalt-manganese ternary material presoma process by Comprehensive Control, the pH value technological parameter of reaction system in reaction temperature and course of reaction, and then forming core speed and the speed of growth of crystal in coprecipitation reaction process have been controlled, make to reach balance between crystal forming core and growth, thereby prepare the nickel-cobalt-manganese ternary material presoma of spherical morphology, the narrow diameter distribution of this nickel-cobalt-manganese ternary material presoma, this nickel-cobalt-manganese ternary material presoma is carried out to lithiumation and can obtain nickel-cobalt-manganese ternary material, the tap density of nickel-cobalt-manganese ternary material prepared by the present invention is high.Nickel-cobalt-manganese ternary material prepared by the present invention can be used as anode material for lithium-ion batteries and uses.Compared with prior art, the present invention is without using complexing agent or surfactant to prepare the nickel-cobalt-manganese ternary material of spherical morphology, and therefore method environmental protection, the cost of preparing nickel-cobalt-manganese ternary material provided by the invention is lower.In addition, preparation method's technique of nickel-cobalt-manganese ternary material provided by the invention is simple, easy and simple to handle.
The explanation of above embodiment is just for helping to understand method of the present invention and core concept thereof.It should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention, can also carry out some improvement and modification to the present invention, these improvement and modification also fall in the protection range of the claims in the present invention.
Claims (10)
1. a preparation method for nickel-cobalt-manganese ternary material, comprises the following steps:
1), under stirring action, under the condition that is 7.5～8.5 in pH value by the soluble-salt of the soluble-salt of the soluble-salt of nickel, cobalt, manganese and precipitation reagent, carry out coprecipitation reaction, obtain nickel-cobalt-manganese ternary material presoma, the speed of described stirring is 600 revs/min～1000 revs/min, and the reaction temperature of described coprecipitation reaction is 40 ℃～60 ℃;
2), described nickel-cobalt-manganese ternary material presoma is calcined, obtain intermediate product;
3), described intermediate product is mixed with lithium source after sintering, obtain nickel-cobalt-manganese ternary material.
2. method according to claim 1, is characterized in that, the speed of described stirring is 700 revs/min～900 revs/min.
3. method according to claim 1, is characterized in that, described pH value is 8.0～8.5.
4. method according to claim 1, is characterized in that, the reaction temperature of described coprecipitation reaction is 45 ℃～55 ℃.
5. method according to claim 1, is characterized in that, the reaction time of described coprecipitation reaction is 6h～12h.
6. method according to claim 1, is characterized in that, the ratio of the molal quantity that the soluble-salt of the soluble-salt of described nickel, the soluble-salt of cobalt and manganese is total and the molal quantity of precipitation reagent is 1:(1～2).
7. method according to claim 1, is characterized in that, described precipitation reagent is one or more in carbonate.
8. method according to claim 1, is characterized in that, described precipitation reagent is precipitant solution, and the molar concentration of described precipitant solution is 1.0mol/L～2.5mol/L.
9. method according to claim 1, is characterized in that, the soluble-salt of described nickel comprises one or more in the halide of nickelous sulfate, nickel nitrate and nickel;
The soluble-salt of described cobalt comprises one or more in the halide of cobaltous sulfate, cobalt nitrate and cobalt;
The soluble-salt of described manganese comprises one or more in the halide of manganese sulfate, manganese nitrate and manganese.
10. an anode material for lithium-ion batteries, nickel-cobalt-manganese ternary material prepared by method described in any one in claim 1～9 is as anode material for lithium-ion batteries.
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104300145A (en) * | 2014-10-10 | 2015-01-21 | 东莞市长安东阳光铝业研发有限公司 | Preparation method for high-tapping-density modified nickel-cobalt lithium manganate positive material |
| CN104934594A (en) * | 2015-04-28 | 2015-09-23 | 湖南兴瑞新材料研究发展有限公司 | Coating modified nickel-cobalt binary material, and preparation method and application of material |
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| CN107221656A (en) * | 2017-06-07 | 2017-09-29 | 北京当升材料科技股份有限公司 | A kind of lithium ion battery rich lithium manganese base solid solution positive electrode and preparation method thereof |
| CN107799741A (en) * | 2017-09-28 | 2018-03-13 | 华南理工大学 | A kind of preparation method of the lithium ion battery nickel-cobalt-manganese ternary positive electrode of modified zinc oxide |
| CN107871863A (en) * | 2017-10-24 | 2018-04-03 | 陈训财 | A kind of method for continuously, quickly preparing nickelic nickel-cobalt-manganese ternary material precursor |
| CN109415225A (en) * | 2016-07-20 | 2019-03-01 | 托普索公司 | Method for precipitating metal carbonate materials particle under without using chelating agent |
| CN110364714A (en) * | 2019-07-17 | 2019-10-22 | 中国恩菲工程技术有限公司 | The method for preparing nickel-cobalt-manganese ternary material precursor |
| CN110752366A (en) * | 2019-10-29 | 2020-02-04 | 广东省稀有金属研究所 | Nickel-cobalt-aluminum hydroxide precursor, preparation method thereof, positive electrode material and battery |
| CN115490277A (en) * | 2022-09-30 | 2022-12-20 | 山东精工电子科技股份有限公司 | Magnetic field modified ternary material for lithium ion battery and preparation method thereof |
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| CN104300145B (en) * | 2014-10-10 | 2017-02-15 | 东莞市长安东阳光铝业研发有限公司 | Preparation method for high-tapping-density modified nickel-cobalt lithium manganate positive material |
| CN104300145A (en) * | 2014-10-10 | 2015-01-21 | 东莞市长安东阳光铝业研发有限公司 | Preparation method for high-tapping-density modified nickel-cobalt lithium manganate positive material |
| CN105810939A (en) * | 2014-12-31 | 2016-07-27 | 北京当升材料科技股份有限公司 | Preparation method of low-sulfur multi-element positive electrode material |
| CN104934594A (en) * | 2015-04-28 | 2015-09-23 | 湖南兴瑞新材料研究发展有限公司 | Coating modified nickel-cobalt binary material, and preparation method and application of material |
| CN109415225A (en) * | 2016-07-20 | 2019-03-01 | 托普索公司 | Method for precipitating metal carbonate materials particle under without using chelating agent |
| US11952287B2 (en) | 2016-07-20 | 2024-04-09 | Haldor Topsøe A/S | Method for the precipitation of particles of a metal carbonate material without use of a chelating agent |
| CN106252649A (en) * | 2016-10-11 | 2016-12-21 | 宁德新能源科技有限公司 | A kind of anode pole piece and the lithium ion battery containing this pole piece |
| CN107221656A (en) * | 2017-06-07 | 2017-09-29 | 北京当升材料科技股份有限公司 | A kind of lithium ion battery rich lithium manganese base solid solution positive electrode and preparation method thereof |
| CN107799741A (en) * | 2017-09-28 | 2018-03-13 | 华南理工大学 | A kind of preparation method of the lithium ion battery nickel-cobalt-manganese ternary positive electrode of modified zinc oxide |
| CN107871863A (en) * | 2017-10-24 | 2018-04-03 | 陈训财 | A kind of method for continuously, quickly preparing nickelic nickel-cobalt-manganese ternary material precursor |
| CN110364714B (en) * | 2019-07-17 | 2021-08-20 | 中国恩菲工程技术有限公司 | Method for preparing nickel-cobalt-manganese ternary material precursor |
| CN110364714A (en) * | 2019-07-17 | 2019-10-22 | 中国恩菲工程技术有限公司 | The method for preparing nickel-cobalt-manganese ternary material precursor |
| CN110752366B (en) * | 2019-10-29 | 2021-07-30 | 广东省稀有金属研究所 | Nickel-cobalt-aluminum hydroxide precursor, preparation method thereof, positive electrode material and battery |
| CN110752366A (en) * | 2019-10-29 | 2020-02-04 | 广东省稀有金属研究所 | Nickel-cobalt-aluminum hydroxide precursor, preparation method thereof, positive electrode material and battery |
| WO2023020063A1 (en) * | 2021-08-17 | 2023-02-23 | 广东邦普循环科技有限公司 | Method for preparing ternary precursor |
| GB2618684A (en) * | 2021-08-17 | 2023-11-15 | Guangdong Brunp Recycling Technology Co Ltd | Method for preparing ternary precursor |
| CN115490277A (en) * | 2022-09-30 | 2022-12-20 | 山东精工电子科技股份有限公司 | Magnetic field modified ternary material for lithium ion battery and preparation method thereof |
| CN115490277B (en) * | 2022-09-30 | 2024-02-13 | 山东精工电子科技股份有限公司 | Magnetic field modified ternary material for lithium ion battery and preparation method thereof |
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