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CN104051724A - Carbon-coated nickel-cobalt lithium manganate positive electrode material and preparation method thereof - Google Patents

Carbon-coated nickel-cobalt lithium manganate positive electrode material and preparation method thereof Download PDF

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Publication number
CN104051724A
CN104051724A CN201410250912.4A CN201410250912A CN104051724A CN 104051724 A CN104051724 A CN 104051724A CN 201410250912 A CN201410250912 A CN 201410250912A CN 104051724 A CN104051724 A CN 104051724A
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carbon
lithium
positive electrode
cobalt
nickel
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刘三兵
朱广燕
梅周盛
卢磊
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Chery Automobile Co Ltd
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Chery Automobile Co Ltd
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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
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • 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
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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
    • 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
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • 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

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Composite Materials (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The embodiment of the invention discloses a preparation method of a carbon-coated nickel-cobalt lithium manganate positive electrode material, and belongs to the technical field of preparation of a lithium battery positive electrode material. The preparation method comprises the following steps: adding a chelating agent and a carbon source into a solution containing lithium salt, nickel salt, cobalt salt and manganese salt, and performing high-temperature spray pyrolysis to obtain precursor powder; compacting the precursor powder by vibration or pressure, wherein the compaction density by the vibration or the pressure is 0.3-3.2g/cm<3> so that lithium ions, nickel ions, cobalt ions and manganese ions are uniformly dispersed in the powder and are contacted closely; and calcining the precursor powder, and cooling to obtain the carbon-coated nickel-cobalt lithium manganate positive electrode material with the good conductivity and the high cyclic stability. The carbon-coated nickel-cobalt lithium manganate positive electrode material comprises nickel-cobalt lithium manganate and carbon coating the surface of nickel-cobalt lithium manganate. The method disclosed by the embodiment of the invention is easy to operate and easy to control and facilitates the large-scale industrial production.

Description

A kind of carbon-coating nickel cobalt manganic acid lithium positive electrode and preparation method thereof
Technical field
The present invention relates to anode material of lithium battery preparing technical field, particularly a kind of carbon-coating nickel cobalt manganic acid lithium positive electrode and preparation method thereof.
Background technology
Due to the pressure of environmental pollution and energy shortage, force various countries to strive to find the new energy and the new vehicles of development.Simultaneously along with the development of information technology, space technology and sophisticated weapon in the urgent need to, caused the miniaturization of electronic equipment, novel electronic equipment constantly comes out again.Battery industry is had higher requirement, and the demand of small-sized high energy, high reliability battery increases sharply.For adapting to this demand, chemical-physical power sources and the system of a large amount of new rangies and new construction are born rapidly and grow up, and lithium ion battery is this product of the time just.Current business-like lithium ion battery mainly adopts LiCoO 2as positive electrode, because cobalt resource rareness, cost are high, contaminated environment and anti-over-charging ability poor, limited the expansion of its application, particularly the application in electrokinetic cell.LiNiO 2specific capacity is large, but while preparation, easily generates the product of non-stoichiometric, the stability of structure and poor heat stability.LiMnO 2specific capacity is slightly large, but it belongs to thermodynamics metastable state, and structural instability exists Jahn-Teller effect, cycle performance poor.Nickel-cobalt lithium manganate cathode material, for example LiNi l/3co 1/3mn l/3o 2combine LiCoO 2, LiNiO 2, LiMnO 2the advantage of three class materials, has made up deficiency separately, has the advantages such as cost is low, specific capacity is high, have extended cycle life, security performance is good.Not only can replace the lithium cobaltate cathode material of applying at present in small portable power supply, and show huge development potentiality at aspects such as high-power lithium ion power batteries, can be used in compact battery and electrokinetic cell, there is wide application market now.
The preparation method of current nickel-cobalt lithium manganate cathode material has a variety of, mainly contains solid phase method, coprecipitation, compound carbonate method, sol-gel process, molten salt growth method, emulsion seasoning and ullrasonic spraying high-temperature decomposition etc.It is short that high temperature solid-state method has technological process, equipment is simple, be easy to the advantages such as large-scale production, but reaction time consumption is long, energy consumption is large, and use solid phase method direct sintering above-mentioned raw materials, easily there is batch mixing inequality, cannot form homogeneous phase eutectic, and the problem such as each batch of product quality be unstable, have a strong impact on chemical property.The synthetic general particle of product of sol-gel process is tiny, and particle diameter is evenly distributed, and crystal property is good, and initial capacity is higher, but synthesis material generally adopts organic reagent, and cost is higher, is difficult to practical application.Coprecipitation, compound carbonate method need the strict reaction condition of controlling, and make each metal ion species synchronous precipitation simultaneously, thereby ensure that in product, each element is evenly distributed, but be difficult to realize, and conventionally can not get desirable ratio.
For instance, prior art is by preparing nickel-cobalt lithium manganate cathode material by compound carbonate method, concrete steps are as follows: soluble nickel salt, cobalt salt, manganese salt are reacted to the compound carbonate that obtains nickel cobalt manganese with precipitation reagent, then this carbonate is reacted with lithium hydroxide, after spraying is dry, obtain the presoma of nickle cobalt lithium manganate, presoma, after twice sintering, obtains nickel-cobalt lithium manganate cathode material.
Inventor finds that prior art at least exists following problem:
Prior art operating process is wayward, and prepared nickel-cobalt lithium manganate cathode material electric conductivity is poor.
Summary of the invention
Technical problem to be solved by this invention is, a kind of carbon-coating nickel cobalt manganic acid lithium positive electrode conducting electricity very well and preparation method simple to operation thereof are provided.In order to solve the problems of the technologies described above, provide following technical scheme:
First aspect, the embodiment of the present invention provides a kind of carbon-coating nickel cobalt manganic acid lithium positive electrode, comprising: nickle cobalt lithium manganate and the carbon that is coated on described nickle cobalt lithium manganate surface.
Particularly, as preferably, the chemical molecular formula of described nickle cobalt lithium manganate is LiNi xco ymn 1-x-yo 2, wherein 0.3≤x <, 1,0.03≤y≤0.5.
Particularly, as preferably, in described carbon-coating nickel cobalt manganic acid lithium positive electrode, the quality percentage composition of described carbon is 0.2%-5%.
As preferably, the quality percentage composition of described carbon is 0.5%-4%.
As preferably, the quality percentage composition of described carbon is 3%.
Particularly, as preferably, the jolt ramming of described carbon-coating nickel cobalt manganic acid lithium positive electrode or compacted density are 0.3g/cm 3-3.2g/cm 3.
As preferably, the jolt ramming of described carbon-coating nickel cobalt manganic acid lithium positive electrode or compacted density are 2.0g/cm 3-3.0g/cm 3.
As preferably, the tap density of described carbon-coating nickel cobalt manganic acid lithium positive electrode is 2.8g/cm 3.
Particularly, as preferably, the particle diameter D50 of described carbon-coating nickel cobalt manganic acid lithium positive electrode is 0.5 μ m-5 μ m.
As preferably, the particle diameter D50 of described carbon-coating nickel cobalt manganic acid lithium positive electrode is 0.5 μ m-3 μ m.
Particularly, as preferably, the specific area of described carbon-coating nickel cobalt manganic acid lithium positive electrode is 0.2m 2/ g-1.1m 2/ g.
As preferably, the specific area of described carbon-coating nickel cobalt manganic acid lithium positive electrode is 0.5m 2/ g-1.0m 2/ g.
As preferably, the specific area of described carbon-coating nickel cobalt manganic acid lithium positive electrode is 0.9m 2/ g.
Second aspect, the embodiment of the present invention provides a kind of carbon-coating nickel cobalt manganic acid lithium positive electrode in the application of preparing in lithium ion battery.
The third aspect, the embodiment of the present invention provides a kind of preparation method of carbon-coating nickel cobalt manganic acid lithium positive electrode, comprising:
Step a, the lithium salts of scheduled volume and/or lithium hydroxide, nickel salt, cobalt salt and manganese salt are dissolved in solvent, obtain the first solution, in described the first solution, add chelating agent and carbon source, mix, obtain the second solution;
Step b, described the second solution is carried out to high-temperature spray pyrolysis, obtain precursor powder, by described precursor powder jolt ramming, making the jolt ramming of described precursor powder or compacted density is 0.3g/cm 3-3.2g/cm 3;
Step c, the described precursor powder after jolt ramming or compacting is calcined, be cooled to room temperature, obtain described carbon-coating nickel cobalt manganic acid lithium positive electrode.
Particularly, as preferably, in described step a, be Li:Ni:Co:Mn=1.01-1.10:x:y:1-x-y according to amount of substance ratio, wherein 0.3≤x < 1,0.03≤y≤0.5, is dissolved in the lithium salts of scheduled volume and/or lithium hydroxide, nickel salt, cobalt salt and manganese salt in solvent, obtains described the first solution.
Particularly, as preferably, total amount of substance of described lithium salts, nickel salt, cobalt salt and manganese salt is 1:1-1:1.2 with the ratio of the amount of substance of described chelating agent.
Particularly, as preferably, in described step a, described solvent is water and/or ethanol.
Particularly, as preferably, in described step a, the concentration of described the first solution is 0.3mol/L-2.5mol/L.
As preferably, the concentration of described the first solution is 0.5mol/L-1.5mol/L.
Particularly, in described step a, described nickel salt is at least one in nickel nitrate, nickel acetate, nickelous sulfate and nickel chloride.
Particularly, in described step a, described cobalt salt is at least one in cobalt nitrate, cobalt acetate, cobaltous sulfate and cobalt chloride.
Particularly, in described step a, described manganese salt is at least one in manganese nitrate, manganese acetate, manganese sulfate and manganese chloride.
Particularly, in described step a, described lithium salts is at least one in lithium nitrate, lithium acetate, lithium chloride and lithium sulfate.
Particularly, in described step a, described chelating agent is at least one in citric acid, glycolic, triethanolamine, acrylic acid and aliphatic acid.
Particularly, in described step a, described carbon source is at least one in citric acid, glycolic, triethanolamine, acrylic acid, aliphatic acid, sucrose, polyvinyl alcohol, glucose, polyacrylonitrile, polyvinyl chloride, phenolic resins and pitch.
Particularly, as preferably, in described step b, the operating temperature of described high-temperature spray pyrolysis is 300-600 DEG C.
As preferably, the operating temperature of high-temperature spray pyrolysis is 400-600 DEG C.
Particularly, as preferably, in described step c, the operating parameter of described calcining is: heating rate is 0.4-12 DEG C/min, and calcining heat is 750-950 DEG C, and calcination time is 3-24h.
As preferably, described heating rate is 3-6 DEG C/min.
As preferably, described calcining heat is 800-900 DEG C.
As preferably, described calcination time is 5-10h.
The beneficial effect that the technical scheme that the embodiment of the present invention provides is brought is:
The embodiment of the present invention provides a kind of carbon-coating nickel cobalt manganic acid lithium positive electrode, comprising: nickle cobalt lithium manganate and be coated on the carbon on described nickle cobalt lithium manganate surface, has improved the conductivity of prepared positive electrode by coated carbon.
The embodiment of the present invention also provides a kind of preparation method of carbon-coating nickel cobalt manganic acid lithium positive electrode, by adding chelating agent and carbon source in the solution to containing lithium salts, nickel salt, cobalt salt and manganese salt, and it is carried out to high-temperature spray pyrolysis, obtain precursor powder, presoma powder is carried out to jolt ramming or compacting, and making its jolt ramming or compacted density is 0.3g/cm 3-3.2g/cm 3, so that lithium, nickel, cobalt and manganese ion being uniformly dispersed in powder, and contact is closely; Then this precursor powder is calcined, conducted electricity very well after cooling, the carbon-coating nickel cobalt manganic acid lithium positive electrode that cyclical stability is high.The method that the embodiment of the present invention provides is simple to operate, easy to control, is easy to large-scale industrial and produces.
Brief description of the drawings
In order to be illustrated more clearly in the technical scheme in the embodiment of the present invention, below the accompanying drawing of required use during embodiment is described is briefly described, apparently, accompanying drawing in the following describes is only some embodiments of the present invention, for those of ordinary skill in the art, do not paying under the prerequisite of creative work, can also obtain according to these accompanying drawings other accompanying drawing.
Fig. 1 is the carbon-coating nickel cobalt manganic acid lithium method for preparing anode material flow chart that embodiment of the present invention provides;
Fig. 2 is the carbon-coating nickel cobalt manganic acid lithium method for preparing anode material flow chart that the another execution mode of the present invention provides;
Fig. 3 is the SEM Electronic Speculum figure of the carbon-coating nickel cobalt manganic acid lithium positive electrode that provides of the embodiment of the present invention 1;
Fig. 4 is the button cell charge-discharge performance resolution chart that the embodiment of the present invention 5 provides;
Fig. 5 is the prior art button cell charge-discharge performance resolution chart that the embodiment of the present invention 5 provides;
The high rate performance resolution chart of the button cell that Fig. 6 embodiment of the present invention 5 provides;
The high rate performance resolution chart of the prior art button cell that Fig. 7 embodiment of the present invention 5 provides.
Embodiment
For making the object, technical solutions and advantages of the present invention clearer, below in conjunction with accompanying drawing, embodiment of the present invention is described further in detail.
First aspect, the embodiment of the present invention provides a kind of carbon-coating nickel cobalt manganic acid lithium positive electrode, comprising: nickle cobalt lithium manganate and the carbon that is coated on described nickle cobalt lithium manganate surface.
The carbon-coating nickel cobalt manganic acid lithium positive electrode that the embodiment of the present invention provides, by the coated one deck carbon of nickle cobalt lithium manganate, improves the conductivity of prepared positive electrode, and then improves the high rate performance of prepared battery.Be understandable that, the carbon-coating nickel cobalt manganic acid lithium positive electrode that the embodiment of the present invention provides, not only there is the advantages such as the cost that nickel-cobalt lithium manganate material brings is low, specific capacity is high, cyclical stability is high, security performance is good, also have that material with carbon element brings conduct electricity very well, reversible specific capacity advantages of higher.
Particularly, the chemical molecular formula of described nickle cobalt lithium manganate is LiNi xco ymn 1-x-yo 2, 0.3≤x <, 1,0.03≤y≤0.5.Wherein, get+divalent of the chemical valence of nickel ion in described nickle cobalt lithium manganate, the chemical valence of cobalt ions is got ﹢ 3 valencys, and the chemical valence of manganese ion is got ﹢ 4 valencys.Above-mentioned LiNi in the embodiment of the present invention xco ymn 1-x-yo 2for layer structure, its specific discharge capacity is high, discharge rate is high, thermally-stabilised height and good cycle, is a kind of positive electrode of function admirable.
Obtain suitable specific area in order to improve the chemical property of prepared carbon-coating nickel cobalt manganic acid lithium positive electrode and to control this positive electrode, the quality percentage composition of carbon described in described carbon-coating nickel cobalt manganic acid lithium positive electrode is defined as 0.2%-5% by the embodiment of the present invention, be preferably 0.5%-4%, more preferably 3%.Further, in order to improve the electric conductivity of prepared positive electrode, described carbon is specially agraphitic carbon or graphite.
Tap density is to weigh an important indicator of positive electrode active materials, because the volume of lithium ion battery is limited, if tap density is too low, in unit volume, the quality of active material is less, makes the energy density of lithium ion battery lower.In order to improve the energy density of lithium battery, in the embodiment of the present invention, the jolt ramming of described carbon-coating nickel cobalt manganic acid lithium positive electrode or compacted density are 0.3g/cm 3-3.2g/cm 3, be preferably 2.0g/cm 3-3.0g/cm 3, more preferably 2.8g/cm 3.
The excessive efflorescence that easily causes active material in charge and discharge process of particle diameter of positive electrode, reduces the cycle performance of positive electrode, and is unfavorable for high power charging-discharging; And particle diameter is too small, can increase granule boundary, cause electric transmission difficulty, increase battery polarization.Based on above-mentioned, in order to ensure the coated good chemical property of nickel-cobalt lithium manganate cathode material, the particle diameter of carbon-coating nickel cobalt manganic acid lithium positive electrode is defined as 0.5 μ m-5 μ m by the embodiment of the present invention, is preferably 0.5 μ m-3 μ m, more preferably 0.2m 2/ g-1.1m 2/ g.
Specific area affects battery high-rate discharge ability, and specific area is larger, and battery high-rate discharge ability is better, but its processing characteristics can be poorer.Based on this, the specific area of carbon-coating nickel cobalt manganic acid lithium positive electrode is defined as 0.5m by the embodiment of the present invention 2/ g-1.0m 2/ g, is preferably 0.9m 2/ g.
Second aspect, the embodiment of the present invention provides a kind of carbon-coating nickel cobalt manganic acid lithium positive electrode in the application of preparing in lithium ion battery.
Prepare lithium ion battery by the carbon-coating nickel cobalt manganic acid lithium positive electrode that the embodiment of the present invention is provided as the anodal active component of lithium ion battery, thereby it is applied in lithium ion battery, and gives the good cycle performance of lithium ion battery and high rate performance.
The third aspect, the embodiment of the present invention provides a kind of preparation method's of carbon-coating nickel cobalt manganic acid lithium positive electrode execution mode, the method flow diagram that accompanying drawing 1 is this execution mode.As shown in Figure 1, the method comprises:
Step 101, the lithium salts of scheduled volume and/or lithium hydroxide, nickel salt, cobalt salt and manganese salt are dissolved in solvent, obtain the first solution, in described the first solution, add chelating agent and carbon source, mix, obtain the second solution.
Step 102, described the second solution is carried out to high-temperature spray pyrolysis, obtain precursor powder, by described precursor powder jolt ramming or compacting, making the jolt ramming of described precursor powder or compacted density is 0.3g/cm 3-3.2g/cm 3.
Step 103, the described precursor powder after jolt ramming or compacting is calcined, be cooled to room temperature, obtain described carbon-coating nickel cobalt manganic acid lithium positive electrode.
The embodiment of the present invention is by adding chelating agent and carbon source in the solution to containing lithium salts, nickel salt, cobalt salt and manganese salt, and it is carried out to high-temperature spray pyrolysis, obtain precursor powder, presoma powder is carried out to jolt ramming or compacting, making its jolt ramming or compacted density is 0.3g/cm 3-3.2g/cm 3, so that lithium, nickel, cobalt and manganese ion being uniformly dispersed in powder, and contact is closely; Then this precursor powder is calcined, conducted electricity very well after cooling, the carbon-coating nickel cobalt manganic acid lithium positive electrode that cyclical stability is high.The method that the embodiment of the present invention provides is simple to operate, easy to control, is easy to large-scale industrial and produces.
Further, the embodiment of the present invention also provides a kind of preparation method's of preferred carbon-coating nickel cobalt manganic acid lithium positive electrode execution mode, the method flow diagram that accompanying drawing 2 is this execution mode.As shown in Figure 2, the method comprises:
Step 201, according to amount of substance than for Li:Ni:Co:Mn=1.01-1.10:x:y:1-x-y, wherein 0.3≤x < 1,0.03≤y < 0.5, the lithium salts of scheduled volume and/or lithium hydroxide, nickel salt, cobalt salt and manganese salt are dissolved in solvent, obtain described the first solution, in described the first solution, add chelating agent and carbon source, mix, obtain the second solution.
Wherein, in step 201, be LiNi in order to obtain molecular formula xco ymn 1-x-yo 2the wherein nickel-cobalt lithium manganate material of 0.3≤x <, 1,0.03≤y≤0.5, is defined as according to amount of substance described scheduled volume than being Li:Ni:Co:Mn=1.01-1.10:x:y:1-x-y, wherein 0.3≤x <, 1,0.03≤y≤0.5.Wherein, in order to compensate a small amount of volatilization of lithium salts in high-temperature calcination process, make the excessive 1%-10% of lithium salts.
Particularly, described nickel salt is at least one in nickel nitrate, nickel acetate, nickelous sulfate and nickel chloride; Described cobalt salt is at least one in cobalt nitrate, cobalt acetate, cobaltous sulfate and cobalt chloride; Described manganese salt is at least one in manganese nitrate, manganese acetate, manganese sulfate and manganese chloride; Described lithium salts is at least one in lithium nitrate, lithium acetate, lithium chloride and lithium sulfate; Described carbon source is at least one in citric acid, glycolic, triethanolamine, acrylic acid, aliphatic acid, sucrose, polyvinyl alcohol, glucose, polyacrylonitrile, polyvinyl chloride, phenolic resins and pitch.
By adding chelating agent, make above-mentioned each metal ion and its formation chelate.Particularly, in the embodiment of the present invention, chelate is selected from least one in citric acid, glycolic, triethanolamine, acrylic acid and aliphatic acid.Chelating agent is final as being present in this positive electrode in the form of the surface coated carbon of nickle cobalt lithium manganate.
For chelating agent is combined whole above-mentioned slaines, and can not cause the chemical property of prepared positive electrode to reduce, in embodiment of the present invention, total amount of substance of described lithium salts, nickel salt, cobalt salt and manganese salt is 1:1-1:1.2 with the ratio of the amount of substance of described chelating agent.
Particularly, the embodiment of the present invention selects the good solvent water of above-mentioned slaine and/or ethanol to dissolve above-mentioned each slaine.More specifically, for the ease of the enforcement of follow-up spray pyrolysis process, embodiment of the present invention is 0.3mol/L-2.5mol/L by the concentration of the first solution, is preferably 0.5mol/L-1.5mol/L.
Step 202, at 300-600 DEG C, described the second solution is carried out to high-temperature spray pyrolysis, obtain precursor powder, by described precursor powder jolt ramming, the tap density that makes described precursor powder is 2.5g/cm 3-3.2g/cm 3.
Embodiment of the present invention promotes that by spray pyrolysis process in the second solution, each raw material carries out thermal decomposition effectively, thereby obtains the micron order uniform particle that sintering character is good.In order further to ensure effective enforcement of thermal decomposition, and do not cause thermal waste, the operating temperature of this high-temperature spray pyrolysis is preferably 400-600 DEG C.
The embodiment of the present invention is by carrying out precursor powder jolt ramming and making its jolt ramming or compacted density remain on 0.3g/cm 3-3.2g/cm 3, not only make in this powder the contact of each raw material closely, the diffusion of each ion while being beneficial to high-temperature calcination, and can improve the dispersing uniformity of lithium ion, nickel ion, cobalt ions and manganese ion in this powder, thus be beneficial to the chemical property that improves positive electrode.
Step 203, be 0.4-12 DEG C/min at heating rate, calcining heat is, under the condition of 750-950 DEG C, the described precursor powder after jolt ramming to be calcined to 3-24h, is cooled to room temperature, obtains described carbon-coating nickel cobalt manganic acid lithium positive electrode.
Calcine by obtaining precursor powder after high-temperature spray pyrolysis, make the further pyrolysis of precursor powder, obtain stable carbon-coating nickel cobalt manganic acid lithium positive electrode.Particularly, carbon is coated on nickel-cobalt lithium manganate material surface.
Further, in order to make in precursor powder each composition pyrolysis complete, improve positive electrode uniform particles degree, the operating parameter of high-temperature calcination is preferably: heating rate is 3-6 DEG C/min, described calcining heat is 800-900 DEG C, and described calcination time is 5-10h.
By specific embodiment, the present invention is described further below.
Embodiment 1
The embodiment of the present invention provide a kind of carbon-coating nickel cobalt manganic acid lithium composite positive pole preparation method, comprise the following steps:
1) accurately take a certain amount of lithium nitrate, nickel acetate, cobalt acetate, manganese acetate according to amount of substance ratio Li:Ni:Co:Mn=3.12:1:1:1, solvent is deionized water, alcohol mixeding liquid (mass ratio of deionized water and ethanol is 1:1), is made into uniform solution.Add citric acid chelating agent, glucose carbon source, carry out magnetic agitation and be uniformly dispersed, obtain transparent mixed solution.Then this solution is carried out to high-temperature spray pyrolysis, pyrolysis temperature is 350 DEG C, obtains precursor powder material.
2), by the jolt ramming of precursor powder material, making its tap density is 0.8g/cm 3, then carry out temperature programmed control air atmosphere sintering, be heated to 800 DEG C with 0.4 DEG C/min programming rate, calcining 24h, is then cooled to room temperature naturally, obtains carbon-coating nickel manganese lithium cobaltate cathode material.
Wherein, in this carbon-coating nickel manganese lithium cobaltate cathode material, the molecular formula of nickle cobalt lithium manganate is LiNi 1/3co 1/3mn 1/3o 2, the quality percentage composition of coated carbon is 0.5%.The average grain diameter that records carbon-coating nickel manganese lithium cobaltate cathode material prepared by the embodiment of the present invention is 1.5-3.5 μ m, and specific area is 0.2m 2/ g.
The structure of the carbon-coating nickel manganese lithium cobaltate cathode material of by ESEM being prepared by the embodiment of the present invention is observed, result as shown in Figure 3, visible, carbon-coating nickel manganese lithium cobaltate cathode material prepared by the embodiment of the present invention 1 is spherical in shape or class is spherical, even particle size, without agglomeration, be beneficial to the chemical property that improves positive electrode.
Embodiment 2
The embodiment of the present invention provide a kind of carbon-coating nickel cobalt manganic acid lithium composite positive pole preparation method, comprise the following steps:
1) accurately take a certain amount of lithium acetate, nickel nitrate, cobalt chloride, manganese chloride according to amount of substance ratio Li:Ni:Co:Mn=1.06:0.3:0.3:0.4, solvent is ethanol, wiring solution-forming.Add triethanolamine chelating agent, phenolic resins carbon source, carry out ball milling and be uniformly dispersed, obtain transparent mixed solution.Then this solution is carried out to high-temperature spray pyrolysis, pyrolysis temperature is 600 DEG C, obtains precursor powder material.
2), by above-mentioned precursor powder material compaction, making its compacted density is 2.5g/cm 3, then carry out temperature programmed control air atmosphere sintering, be heated to 950 DEG C with 5 DEG C/min programming rate, calcining 6h, is then cooled to room temperature naturally, obtains the coated nickel manganese lithium cobaltate cathode material of carbon.
Wherein, in this carbon-coating nickel manganese lithium cobaltate cathode material, the molecular formula of nickle cobalt lithium manganate is LiNi 0.3co 0.3mn 0.4o 2, the quality percentage composition of coated carbon is 3%.The average grain diameter that records carbon-coating nickel manganese lithium cobaltate cathode material prepared by the embodiment of the present invention is 1-2.5 μ m, and specific area is 0.9m 2/ g.
Embodiment 3
The embodiment of the present invention provide a kind of carbon-coating nickel cobalt manganic acid lithium composite positive pole preparation method, comprise the following steps:
1) accurately take a certain amount of lithium hydroxide, nickelous sulfate, cobaltous sulfate, manganese sulfate according to amount of substance ratio Li:Ni:Co:Mn=1.10:0.6:0.03:0.37, solvent is deionized water, wiring solution-forming.Add aliphatic acid chelating agent, aliphatic acid carbon source, carry out ultrasonic being uniformly dispersed, obtain transparent mixed solution.Then high-temperature spray pyrolysis, pyrolysis temperature is 300 DEG C, obtains precursor powder material.
2) above-mentioned precursor powder material is carried out to compacting, making its compacted density is 3.0g/cm 3.Then the powder body material after this compacting is in fact carried out to temperature programmed control air atmosphere sintering, be heated to 750 DEG C with 6 DEG C/min programming rate, calcining 10h, is then cooled to room temperature naturally, obtains carbon-coating nickel manganese lithium cobaltate cathode material.
Wherein, in this carbon-coating nickel manganese lithium cobaltate cathode material, the molecular formula of nickle cobalt lithium manganate is LiNi 0.6co 0.03mn 0.37o 2, the quality percentage composition of coated carbon is 0.2%.The average grain diameter that records carbon-coating nickel manganese lithium cobaltate cathode material prepared by the embodiment of the present invention is 0.5-1.5 μ m, and specific area is 0.5m 2/ g.
Embodiment 4
The embodiment of the present invention provide a kind of carbon-coating nickel cobalt manganic acid lithium composite positive pole preparation method, comprise the following steps:
1) accurately take a certain amount of lithium sulfate, nickel chloride, cobaltous sulfate, manganese chloride according to amount of substance ratio Li:Ni:Co:Mn=1.01:0.4:0.5:0.1, solvent is deionized water, wiring solution-forming.Add acrylic acid chelating agent, sucrose carbon source, carry out magnetic agitation it is uniformly dispersed, obtain transparent mixed solution.Then this mixed solution is carried out to high-temperature spray pyrolysis, pyrolysis temperature is 400 DEG C, obtains precursor powder material.
2) above-mentioned precursor powder material is carried out to compacting, making its compacted density is 3.2g/cm 3.Powder body material after this compacting is carried out to temperature programmed control air atmosphere sintering, be heated to 850 DEG C with 12 DEG C/min programming rate, calcining 3h, is then cooled to room temperature naturally, obtains carbon-coating nickel manganese lithium cobaltate cathode material.
Wherein, in this carbon-coating nickel manganese lithium cobaltate cathode material, the molecular formula of nickle cobalt lithium manganate is LiNi 0.4co 0.5mn 0.1o 2, coated carbonaceous amount percentage composition is 5%.The average grain diameter that records carbon-coating nickel manganese lithium cobaltate cathode material prepared by the embodiment of the present invention is 4.5-5 μ m, and specific area is 1.1m 2/ g.
Embodiment 5
The present embodiment utilizes carbon-coating nickel manganese lithium cobaltate cathode material prepared by the embodiment of the present invention 1 to prepare lithium ion battery, and step is as follows:
Carbon-coating nickel manganese lithium cobaltate cathode material prepared by embodiment 1 mixes according to mass ratio 8:1:1 with conductive agent acetylene black, binding agent PVDF (Kynoar), this mixture is modulated into slurry with NMP (1-Methyl-2-Pyrrolidone), evenly be coated on aluminium foil, put into baking oven, dry 3h for 110 DEG C, take out and be washed into pole piece, 85 DEG C of vacuumize 12 hours, carry out compressing tablet, 85 DEG C of vacuumize 12 hours, makes experimental cell pole piece.
Then taking lithium sheet as to electrode, 1.2mol/L LiPF 6eC (ethyl carbonate ester)+DMC (dimethyl carbonate) (volume ratio 1:1) solution be electrolyte, celgard2400 film is barrier film, is assembled into CR2025 type button cell in the glove box that is full of argon gas atmosphere.
Then the button cell of above-mentioned preparation is carried out to charge-discharge performance test, wherein, charging/discharging voltage scope is 4.3～2.75V, and charging and discharging currents is the lower circulation of 0.1C (1C=150mA/g) 6 times, then keeps charging and discharging currents to be 0.2C.Result is as shown in Figure 4: under the condition of 0.2C charging or discharging current, the specific discharge capacity of circulation first of the prepared lithium ion battery of the carbon-coating nickel manganese lithium cobaltate cathode material that utilizes the embodiment of the present invention 1 to prepare is 153.9667mAh/g, the specific discharge capacity after 50 times that circulates is 149.983mAh/g, and capability retention is 97.4%.
Under same operating condition, be LiNi to the prepared molecular formula of prior art 1/3co 1/3mn 1/3o 2nickel-cobalt lithium manganate cathode material carry out cycle performance test, result is as shown in Figure 5: under the condition of 0.2C charging or discharging current, the specific discharge capacity of circulation first of the nickel-cobalt lithium manganate cathode material that prior art provides is 147.25mAh/g, 50 specific discharge capacities that circulate are 137.214mAh/g, and capability retention is 93.18%.Visible, compared to existing technology, the cyclical stability of carbon-coating nickel cobalt manganic acid lithium positive electrode prepared by the embodiment of the present invention 1 is better.
Be 4.3～2.75V in charging/discharging voltage scope, charging current is 0.1C, discharging current is respectively 0.1C, 0.2C, 0.5C, 1C, 2C, 5C, 10C, under the condition that each multiplying power circulation is 5 times, the high rate performance of the above-mentioned battery that the battery of respectively being prepared by the present embodiment and prior art provide is tested, test result is distinguished as shown in FIG. 6 and 7: the first discharge specific capacity that the prepared lithium ion battery of carbon-coating nickel manganese lithium cobaltate cathode material that utilizes the embodiment of the present invention 1 to prepare discharges and recharges under condition at 0.1C is 156.098mAh/g, 10C discharges and recharges still more than 108mAh/g (referring to the Fig. 6) of specific discharge capacity under condition.And the first discharge specific capacity that the nickel manganese lithium cobaltate cathode material that prior art provides discharges and recharges under condition at 0.1C is 160.718Ah/g, the specific discharge capacity that 10C discharges and recharges under condition is about 99mAh/g (referring to Fig. 7).Visible, compared to existing technology, the high rate performance of carbon-coating nickel cobalt manganic acid lithium positive electrode prepared by the embodiment of the present invention 1 is better.
Embodiment 6
The present embodiment utilizes carbon-coating nickel cobalt manganic acid lithium positive electrode prepared by embodiment of the present invention 2-4 to prepare lithium ion battery, and the charge-discharge performance of prepared battery is tested.Concrete operating procedure and operating parameter are identical with embodiment 5.Result is as shown in table 1:
The charge-discharge performance parameter testing list of table 1 battery
As shown in Table 1, above-mentioned each battery all shows excellent cyclical stability, visible, and the carbon-coating nickel cobalt manganic acid lithium positive electrode prepared by method provided by the invention has a good application prospect in lithium ion battery preparation field.And method provided by the invention is simple to operate, easy to control, is beneficial to large-scale industrial and produces.
The foregoing is only preferred embodiment of the present invention, in order to limit the scope of the invention, within the spirit and principles in the present invention not all, any amendment of doing, be equal to replacement, improvement etc., within all should being included in protection scope of the present invention.

Claims (10)

1. a carbon-coating nickel cobalt manganic acid lithium positive electrode, comprising: nickle cobalt lithium manganate and the carbon that is coated on described nickle cobalt lithium manganate surface.
2. carbon-coating nickel cobalt manganic acid lithium positive electrode according to claim 1, is characterized in that, the chemical molecular formula of described nickle cobalt lithium manganate is LiNi xco ymn 1-x-yo 2, wherein 0.3≤x <, 1,0.03≤y≤0.5.
3. carbon-coating nickel cobalt manganic acid lithium positive electrode according to claim 1, is characterized in that, in described carbon-coating nickel cobalt manganic acid lithium positive electrode, the quality percentage composition of described carbon is 0.2%-5%.
4. according to the carbon-coating nickel cobalt manganic acid lithium positive electrode described in claim 1-3 any one, it is characterized in that, the jolt ramming of described carbon-coating nickel cobalt manganic acid lithium positive electrode or compacted density are 0.3g/cm 3-3.2g/cm 3.
5. the carbon-coating nickel cobalt manganic acid lithium positive electrode described in a claim 1-4 any one is in the application of preparing in lithium ion battery.
6. a preparation method for carbon-coating nickel cobalt manganic acid lithium positive electrode, comprising:
Step a, the lithium salts of scheduled volume and/or lithium hydroxide, nickel salt, cobalt salt and manganese salt are dissolved in solvent, obtain the first solution, in described the first solution, add chelating agent and carbon source, mix, obtain the second solution;
Step b, described the second solution is carried out to high-temperature spray pyrolysis, obtains precursor powder, by described precursor powder jolt ramming or compacting, make described precursor powder or compacted density be 0.3g/cm 3-3.2g/cm 3;
Step c, the described precursor powder after jolt ramming or compacting is calcined, be cooled to room temperature, obtain described carbon-coating nickel cobalt manganic acid lithium positive electrode.
7. method according to claim 6, is characterized in that, in described step a, described nickel salt is at least one in nickel nitrate, nickel acetate, nickelous sulfate and nickel chloride; Described cobalt salt is at least one in cobalt nitrate, cobalt acetate, cobaltous sulfate and cobalt chloride; Described manganese salt is at least one in manganese nitrate, manganese acetate, manganese sulfate and manganese chloride; Described lithium salts is at least one in lithium nitrate, lithium acetate, lithium chloride and lithium sulfate.
8. method according to claim 6, is characterized in that, in described step a, described chelating agent is at least one in citric acid, glycolic, triethanolamine, acrylic acid and aliphatic acid; Described carbon source is at least one in citric acid, glycolic, triethanolamine, acrylic acid, aliphatic acid, sucrose, polyvinyl alcohol, glucose, polyacrylonitrile, polyvinyl chloride, phenolic resins and pitch.
9. method according to claim 6, is characterized in that, in described step b, the operating temperature of described high-temperature spray pyrolysis is 300-600 DEG C.
10. method according to claim 6, is characterized in that, in described step c, the operating parameter of described calcining is: heating rate is 0.4-12 DEG C/min, and calcining heat is 750-950 DEG C, and calcination time is 3-24h.
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