CN103746108B - The preparation method of Hollow Nickel LiMn2O4 structure doped lithium ion battery cathode material - Google Patents

The preparation method of Hollow Nickel LiMn2O4 structure doped lithium ion battery cathode material Download PDF

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CN103746108B
CN103746108B CN201310719639.0A CN201310719639A CN103746108B CN 103746108 B CN103746108 B CN 103746108B CN 201310719639 A CN201310719639 A CN 201310719639A CN 103746108 B CN103746108 B CN 103746108B
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hollow
preparation
nickel
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core construction
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CN103746108A (en
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蓝凌霄
吴汉杰
黄美红
赵玉超
梁兴华
史琳
刘于斯
曾帅波
叶超超
刘天骄
华晓鸣
宋清清
刘浩
刘大玉
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Guangxi University of Science and Technology
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/362Composites
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/362Composites
    • H01M4/366Composites as layered products
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/48Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505Selection 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
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/48Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525Selection 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
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/052Li-accumulators
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

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

Abstract

The invention provides a kind of preparation method of Hollow Nickel LiMn2O4 structure doped lithium ion battery cathode material, comprise following step: 1, the preparation of carbon ball; 2, the preparation of magnesium Hollow Nickel LiMn2O4 is mixed; 3, the preparation that the nickel ion doped of magnesium-doped hollow-core construction is coated.The invention enables the cycle life of battery to obtain to promote greatly, and cycle efficieny remains on about 90%.

Description

The preparation method of Hollow Nickel LiMn2O4 structure doped lithium ion battery cathode material
Technical field
The present invention relates to the preparation method in a kind of cell positive material, particularly relate to a kind of preparation of hollow ball structure nickel ion doped material, nickel ion doped doping and surface coated method.
Background technology
Nickel ion doped surface is directly contact with electrolyte, Mn in nickel ion doped material 3+soluble in electrolyte is molten, poor electric conductivity, the utilance of material are low, lithium ion diffusion is slow, cause that the reversibility of battery is poor thus, the problem such as cycle performance difference in cyclic process under capability retention low and high temperature or under large multiplying power.One of common solution, doping and Li in nickel ion doped material +, Ni 2+, Mn 4+, O 2-other ions that plasma effect power is stronger occupy relevant position, be combined with O and form the chemical bond more stable than Mn-O bond energy and carry out stable nickel ion doped lattice structure, effectively suppress because Mn3+ is dissolved in the problem that electrolyte makes nickel ion doped lattice subside, thus capability retention in the reversibility of battery and cyclic process can be improved; Its solution two, at the protective material that Surface coating one deck and the electrolyte of nickel ion doped material directly contact, can have and suppress the metal ion of high-valence state to the oxidation of electrolyte, make electrolyte more stable, can also stop Mn in certain degree 3+stripping, while playing protective material stability action, the stability in the cyclic process under the conductivity of material, high temperature can also be improved or under large multiplying power and capability retention.Utilance for nickel ion doped is low spreads slow problem with lithium ion, nickel ion doped is prepared into hollow-core construction, can greatly reduces the distance that lithium ion shuttles back and forth like this, improve the utilance of material.
But in current technology, the nickel ion doped size of hollow-core construction differs; The nickel ion doped of hollow-core construction is adulterated, the particular location adulterated can not be guaranteed; Carry out Surface coating to the nickel ion doped of hollow-core construction, the thickness evenness of the area size that coating layer is coated and coating layer differs.
Summary of the invention
In order to solve above technical problem.The method of multiple performance change is applied in nickel ion doped material by the present invention simultaneously, and breach the mode of thinking in the past only changing a kind of performance by single mode, make the performance of material have more advantage, concrete operation step is as follows:
Steps A: the preparation of carbon ball: glucose is dissolved in deionized water, high-speed stirred to solution presents clarification shape, again solution is transferred in reactor, reaction 10 to 14 hours at 160 DEG C to 200 DEG C again, naturally cool to room temperature again, product in reactor is used respectively deionized water, absolute ethyl alcohol centrifuge washing, dextrose components remaining in removing product, then after vacuumize, obtain the carbon ball of black.
Step B: nickel acetate and manganese acetate are dissolved in absolute ethyl alcohol, again concentrated hydrochloric acid is slowly added drop-wise to magnetic agitation in solution, 1-1.5mol/L carbon ball is added again in this system, with ultrasonic echography until form homogeneous state, again product is transferred to 160 DEG C to 200 DEG C constant temperature 6-10 hour in reactor, after complete reaction, naturally cool to the sediment that room temperature obtains black, again respectively deionized water is used to black precipitate, absolute ethyl alcohol centrifuge washing, remove non-impurity, the presoma of carbon/nickel oxide is obtained after vacuumize, presoma is transferred in Muffle furnace, 3-5 hour is calcined under 500-700 DEG C of constant temperature, obtain the Ni, Mn oxide of hollow-core construction.
Step C: lithium acetate, magnesium acetate are all dissolved in absolute ethyl alcohol, according to the ratio of amount of substance in chemical molecular formula, namely the ratio of lithium acetate and magnesium acetate amount of substance is 1.1:2, wherein lithium acetate consumption have 10% excessive, be used for the loss made up in sintering process, the Ni, Mn oxide of hollow-core construction is added in the solution of lithium acetate, with ultrasonic echography until form homogeneous state, continue ultrasonic absolute ethyl alcohol to be evaporated, then be transferred in Muffle furnace and carry out solid phase reaction, calcining at constant temperature, obtains the nickel ion doped of the hollow-core construction doped with magnesium;
Step D: the preparation that the nickel ion doped of magnesium-doped hollow-core construction is coated: is slowly dripped ammoniacal liquor under the state that liquor argenti nitratis ophthalmicus is stirred, until the precipitation generated is dissolved just completely present transparence, be heated to 65-85 DEG C and carry out water-bath, the nickel ion doped powder mixing magnesium hollow-core construction prepared by described step C is dissolved in absolute ethyl alcohol and adds thermal agitation, with ultrasonic cleaner, solution is disperseed simultaneously, add 5mL formaldehyde, liquor argenti nitratis ophthalmicus is slowly joined in this solution, stirring makes it fully react, to product deionized water centrifuge washing, the nickel ion doped composite material mixing magnesium hollow-core construction that silver is coated is obtained after vacuumize.
Wherein, the amount that formaldehyde and liquor argenti nitratis ophthalmicus add makes it fully silver mirror reaction occur.
Preferably, in described steps A and B, in vacuum drying chamber under 60 DEG C of constant temperature dry 6 hours.
Preferably, the temperature of calcining under constant temperature is 800 DEG C, and the time is 6 hours.
Preferably, in described step D, the concentration of liquor argenti nitratis ophthalmicus is 0.2mol/L.
Preferably, in described step D, add the time of formaldehyde for latter 5 to 15 minutes of dispersion.
Preferably, in described step D, the temperature of vacuum drying chamber is 100 DEG C.
Preferably, carbon ball with the ratio of the amount of substance of nickel acetate is: 1-1.5.
Preferably, the ratio of lithium acetate and manganese acetate amount of substance is 1.1:2, wherein lithium acetate consumption have 10% excessive, be used for the loss made up in sintering process.
In this invention, consider the situation that the size of hollow-core construction nickel ion doped differs, then carbon ball is screened, the size of its carbon ball is controlled within the scope of uniformity, control the uniformity of hollow-core construction nickel ion doped scantling, and substantially increase the efficiency of lithium ion in deintercalation and inserting process, make the utilance of material improve, the actual specific capacity (140mAh/g) of material is almost close to theoretical values (146.7mAh/g); Actual magnesium-doped position can not be clear and definite, but can know magnesium approximate location in nickel ion doped structure by computer sim-ulation; For the thickness problem of coated areal extent, coating layer, then by extend reaction time, temperature, high-speed stirred reaction mode solve, under coating layer restrained effectively the condition of high temperature, the resolution problem of battery electrolyte, the cycle life of battery is obtained promote greatly, and cycle efficieny remains on about 90%.
Accompanying drawing explanation
Fig. 1 is the hollow-core construction nickel ion doped schematic diagram that the present invention prepares.
Fig. 2 is the SEM figure of the hollow-core construction nickel ion doped in an embodiment of the present invention.
Fig. 3 be the present invention adulterate and coated after nickel ion doped structural representation.
Fig. 4 be hollow-core construction nickel ion doped of the present invention doping and coated after SEM figure.
Fig. 5 be hollow-core construction nickel ion doped of the present invention doping and coated after charge and discharge cycles curve.
Fig. 6 be hollow-core construction nickel ion doped of the present invention doping and coated after 100 charge and discharge cycles curves.
Embodiment
Below in conjunction with accompanying drawing, preferably embodiment of the present invention is described in further detail:
Embodiment 1:
1, the preparation of carbon ball
Be dissolved in deionized water by the glucose of 9g, solution until solution presents clarification shape, then is transferred in the reactor of 100mL by high-speed stirred half an hour, isothermal reaction 12 hours under the environment of 180 DEG C.When by the time naturally cooling to room temperature, the product in reactor is used respectively deionized water, absolute ethyl alcohol centrifuge washing three times, dextrose components remaining in removing product.In vacuum drying chamber under 60 DEG C of constant temperature dry 6 hours, the carbon ball of black will be obtained.
2, the preparation of magnesium Hollow Nickel LiMn2O4 is mixed
1. the nickel acetate of 0.5mol, the manganese acetate of 1.5mol are dissolved in the absolute ethyl alcohol of 40mL, then concentrated hydrochloric acid are slowly added drop-wise in solution magnetic agitation 10 minutes, then in this system, add the carbon ball of 1mol, with ultrasonic echography until form homogeneous state.The product of above-mentioned system to be transferred in the reactor of 100mL 180 ° of constant temperature 8 hours.After complete reaction, when naturally cooling to room temperature, obtain the sediment of black.Deionized water, absolute ethyl alcohol centrifuge washing three times are used respectively to black precipitate, removes the impurity failing to participate in reaction.In vacuum drying chamber under 60 DEG C of constant temperature dry 6 hours, obtain the presoma of carbon/nickel oxide.Presoma is transferred in Muffle furnace, calcine 4 hours under 600 DEG C of constant temperature, obtain the Ni, Mn oxide of hollow-core construction.
2. lithium acetate, magnesium acetate are all dissolved in absolute ethyl alcohol, according to the ratio of 1.1:2 amount of substance, the Ni, Mn oxide of hollow-core construction is added in the solution of lithium acetate, with ultrasonic echography until form homogeneous state, continue ultrasonic absolute ethyl alcohol to be evaporated, then be transferred in Muffle furnace and carry out solid phase reaction, calcine 6 hours under 800 DEG C of constant temperature, finally obtain the nickel ion doped of the hollow-core construction doped with magnesium.
3, the preparation that the nickel ion doped of magnesium-doped hollow-core construction is coated
The liquor argenti nitratis ophthalmicus of configuration 0.2mol/L, slowly drips ammoniacal liquor under the state that magnetic stirring apparatus stirs, until the precipitation generated is dissolved just completely present transparence, is heated to 75 DEG C and carries out water-bath.The nickel ion doped powder mixing magnesium hollow-core construction prepared on top is dissolved in absolute ethyl alcohol and adds thermal agitation, disperses with ultrasonic cleaner to solution simultaneously, disperses the formaldehyde adding 5mL after 10 minutes.Slowly joined by liquor argenti nitratis ophthalmicus in this solution, magnetic agitation 30 minutes, makes it fully react.To product deionized water centrifuge washing three times, dry under 100 DEG C of constant temperature in vacuum drying chamber, finally obtain the nickel ion doped composite material mixing magnesium hollow-core construction that silver is coated.
Embodiment 2
1, the preparation of carbon ball
Be dissolved in by the glucose of 13.5g in a certain amount of deionized water, solution until solution presents clarification shape, then is transferred in the reactor of 100mL by high-speed stirred half an hour, isothermal reaction 10 hours under the environment of 2000 DEG C.When by the time naturally cooling to room temperature, the product in reactor is used respectively deionized water, absolute ethyl alcohol centrifuge washing three times, dextrose components remaining in removing product.In vacuum drying chamber under 60 DEG C of constant temperature dry 6 hours, the carbon ball of black will be obtained.
2, the preparation of magnesium Hollow Nickel LiMn2O4 is mixed
1. the nickel acetate of 0.75mol, the manganese acetate of 7.5mol are dissolved in the absolute ethyl alcohol of 40mL, then concentrated hydrochloric acid are slowly added drop-wise in solution magnetic agitation 10 minutes, then in this system, add 1.5mol carbon ball, with ultrasonic echography until form homogeneous state.The product of above-mentioned system to be transferred in the reactor of 100mL 200 DEG C of constant temperature 6 hours.After complete reaction, when naturally cooling to room temperature, obtain the sediment of black.Deionized water, absolute ethyl alcohol centrifuge washing three times are used respectively to black precipitate, removes the impurity failing to participate in reaction.In vacuum drying chamber under 60 DEG C of constant temperature dry 6 hours, obtain the presoma of carbon/nickel oxide.Presoma is transferred in Muffle furnace, calcine 4 hours under 600 DEG C of constant temperature, obtain the Ni, Mn oxide of hollow-core construction;
2. lithium acetate, magnesium acetate are all dissolved in absolute ethyl alcohol, according to the ratio of 1.1:2 amount of substance, the Ni, Mn oxide of hollow-core construction is added in the solution of lithium acetate, with ultrasonic echography until form homogeneous state, continue ultrasonic absolute ethyl alcohol to be evaporated, then be transferred in Muffle furnace and carry out solid phase reaction, calcine 6 hours under 800 DEG C of constant temperature, finally obtain the nickel ion doped of the hollow-core construction doped with magnesium.
3, the preparation that the nickel ion doped of magnesium-doped hollow-core construction is coated
The liquor argenti nitratis ophthalmicus of configuration 0.2mol/L, slowly drips ammoniacal liquor under the state that magnetic stirring apparatus stirs, until the precipitation generated is dissolved just completely present transparence, is heated to 80 DEG C and carries out water-bath.The nickel ion doped powder mixing magnesium hollow-core construction prepared on top is dissolved in absolute ethyl alcohol and adds thermal agitation, disperses with ultrasonic cleaner to solution simultaneously, disperses the formaldehyde adding 5mL after 10 minutes.Slowly joined by liquor argenti nitratis ophthalmicus in this solution, magnetic agitation 30 minutes, makes it fully react.To product deionized water centrifuge washing three times, dry under 100 DEG C of constant temperature in vacuum drying chamber, finally obtain the nickel ion doped composite material mixing magnesium hollow-core construction that silver is coated.
The innovation of this programme and other schemes is as follows:
1, the nickel ion doped of preparation is different from traditional entity structure, and what prepare in this programme is hollow-core construction, and the granular size prepared is homogeneous, and covered effect is good, and its schematic diagram and SEM master drawing are as illustrated in fig. 1 and 2.
2, the nickel ion doped material prepared has embodied very large advantage on capacity and cycle life and efficiency thereof, as shown in Fig. 3 to 6, the specific capacity of actual test is at 140mAh/g, this and theoretic 146.7mAh/g very close to, and the platform occurred at 4.1V place obviously reduces, and the charge and discharge platform occurred at about 4.75V is very wide.Especially in charge and discharge cycles process, cycle efficieny remains on about 90%, and consumption rate is lower, and the utilance of material is higher.
Above content is in conjunction with concrete preferred implementation further description made for the present invention, can not assert that specific embodiment of the invention is confined to these explanations.For general technical staff of the technical field of the invention, without departing from the inventive concept of the premise, some simple deduction or replace can also be made, all should be considered as belonging to protection scope of the present invention.

Claims (6)

1. a preparation method for Hollow Nickel LiMn2O4 structure doped lithium ion battery cathode material, is characterized in that, comprises following step:
Steps A: the preparation of carbon ball: glucose is dissolved in deionized water, high-speed stirred to solution presents clarification shape, again solution is transferred in reactor, reaction 10 to 14 hours at 160 DEG C to 200 DEG C again, naturally cool to room temperature again, product in reactor is used respectively deionized water, absolute ethyl alcohol centrifuge washing, glucose remaining in removing product, then after vacuumize, obtain the carbon ball of black;
Step B: nickel acetate and manganese acetate are dissolved in absolute ethyl alcohol, again concentrated hydrochloric acid is slowly added drop-wise to magnetic agitation in solution, carbon ball is added again in this system, with ultrasonic echography until form homogeneous state, again product is transferred to 160 DEG C to 200 DEG C constant temperature 6-10 hour in reactor, after complete reaction, naturally cool to the sediment that room temperature obtains black, again respectively deionized water is used to black precipitate, absolute ethyl alcohol centrifuge washing, remove the impurity failing to participate in reaction, the presoma of carbon/nickel oxide is obtained after vacuumize, presoma is transferred in Muffle furnace, 3-5 hour is calcined under 500-700 DEG C of constant temperature, obtain the Ni, Mn oxide of hollow-core construction,
Step C: lithium acetate, magnesium acetate are all dissolved in absolute ethyl alcohol, again the Ni, Mn oxide of hollow-core construction is added in the solution of lithium acetate, with ultrasonic echography until form homogeneous state, continue ultrasonic absolute ethyl alcohol to be evaporated, then be transferred in Muffle furnace and carry out solid phase reaction, calcining at constant temperature, obtains the nickel ion doped of the hollow-core construction doped with magnesium;
Step D: the preparation that the nickel ion doped of doped hollow structure is coated: is slowly dripped ammoniacal liquor under the state that liquor argenti nitratis ophthalmicus is stirred, until the precipitation generated is dissolved just completely present transparence, be heated to 65-85 DEG C and carry out water-bath, the nickel ion doped powder mixing magnesium hollow-core construction prepared by described step D is dissolved in absolute ethyl alcohol and adds thermal agitation, with ultrasonic cleaner, solution is disperseed simultaneously, add formaldehyde, liquor argenti nitratis ophthalmicus is slowly joined in this solution, stirring makes it fully react, to product deionized water centrifuge washing, the nickel ion doped composite material mixing magnesium hollow-core construction that silver is coated is obtained after vacuumize, in described step B, carbon ball with the ratio of the amount of substance of nickel acetate is: 1-1.5:1, in described step B, the ratio of lithium acetate and manganese acetate amount of substance is 1.1:2.
2. the preparation method of Hollow Nickel LiMn2O4 structure doped lithium ion battery cathode material as claimed in claim 1, is characterized in that, in described steps A and B, and in vacuum drying chamber under 60 DEG C of constant temperature dry 6 hours.
3. the preparation method of Hollow Nickel LiMn2O4 structure doped lithium ion battery cathode material as claimed in claim 1, it is characterized in that, the temperature of calcining under constant temperature is 800 DEG C, and the time is 6 hours.
4. the preparation method of Hollow Nickel LiMn2O4 structure doped lithium ion battery cathode material as claimed in claim 1, it is characterized in that, in described step D, the concentration of liquor argenti nitratis ophthalmicus is 0.2mol/L.
5. the preparation method of Hollow Nickel LiMn2O4 structure doped lithium ion battery cathode material as claimed in claim 1, is characterized in that, in described step D, adds the time of formaldehyde for latter 5 to 15 minutes of dispersion.
6. the preparation method of Hollow Nickel LiMn2O4 structure doped lithium ion battery cathode material as claimed in claim 1, it is characterized in that, in described step D, the temperature of vacuum drying chamber is 100 DEG C.
CN201310719639.0A 2013-12-20 2013-12-20 The preparation method of Hollow Nickel LiMn2O4 structure doped lithium ion battery cathode material Expired - Fee Related CN103746108B (en)

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