CN109378463A - Composite cathode material for lithium ion cell and preparation method thereof - Google Patents
Composite cathode material for lithium ion cell and preparation method thereof Download PDFInfo
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- CN109378463A CN109378463A CN201811421018.3A CN201811421018A CN109378463A CN 109378463 A CN109378463 A CN 109378463A CN 201811421018 A CN201811421018 A CN 201811421018A CN 109378463 A CN109378463 A CN 109378463A
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- lithium ion
- ketjen black
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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
- H01M4/364—Composites as mixtures
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G45/00—Compounds of manganese
- C01G45/12—Manganates manganites or permanganates
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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- 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
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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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The present invention provides a kind of composite cathode material for lithium ion cell and preparation method thereof, by by Bi2Mn4O10After powder and the mixing of Ketjen black (ECP)-N composite material, solvent is added, obtains Bi through ball milling2Mn4O10/ Ketjen black (ECP)-N material precursor, then Bi is made through calcining2Mn4O10/ Ketjen black (ECP)-N composite cathode material for lithium ion cell；Obtained material has excellent high rate performance and stable circulation performance, and ball milling is at room temperature.The method of the invention is easy to operate, low in cost, low energy consumption, environmental-friendly, is suitble to lithium ion battery practical application and industrial-scale production.
Description
Technical field
The present invention relates to battery material technical fields, and in particular to a kind of composite cathode material for lithium ion cell and its preparation
A kind of method, more particularly, to Bi2Mn4O10/ Ketjen black-N composite cathode material for lithium ion cell and preparation method thereof.
Background technique
The big theme of the three of 21st century scientific technological advance is the energy, environment and information, wherein the scarcity of the energy and
Serious problem of environmental pollution has become two hang-ups urgently to be resolved.In order to cope with two above problem, people are dedicated to
Develop solar energy, the novel green clean energy resource such as wind energy and tide energy, to gradually replace non-renewable and to cause ring
The chemical class A fuel A of border pollution.But most of clean energy resource through utilizing all be it is non-controllable and intermittent, lead
The increased costs of energy storage and management are caused, the research and development of energy storage material and energy storage device become the great approach for solving energy problem
One of.
Traditional energy storage device is mainly lead-acid battery and chromium nickel-based battery, but the energy density of lead-acid battery and chromium nickel-based battery
Lower, discarded battery is easy to pollute the environment；And lithium ion battery has voltage height, using the time is long, capacity is big, body
The advantages that accumulating small, memory-less effect and having a safety feature, is just gradually replacing lead-acid battery and chromium nickel-based battery, is becoming concerned by people
Focus.With the fast development of portable electronic device rapid proliferation and electric car, natural graphite cathode in lithium ion battery
Material is no longer satisfied requirement of the electrical equipment to energy density and power density, therefore, develops lithium ion battery of new generation
It is extremely urgent to improve performance of lithium ion battery for negative electrode material.
Transition metal oxide is widely studied because it is with high specific capacity in field of lithium ion battery.In crowd
In more transition metal oxides, Bi2Mn4O10Since initial specific capacities with higher, high tap density and energy are close
Degree, environmental-friendly and at low cost advantage become potential lithium ion battery negative material of new generation.But it is most of
Metal oxide electronic conductivity and ionic conductivity it is all poor, it is poor so as to cause its high rate performance.Meanwhile
In duplicate charge and discharge process, the biggish volume change of metal oxide can reduce the cyclical stability of material.Therefore, how to mention
The electronic conductivity and cyclical stability of high metal oxide are the huge challenges to researcher, currently, reducing particle ruler
Very little, cladding or doping conductive materials are the main means for improving material electrochemical performance.
Summary of the invention
For above-mentioned technical problem in the related technology, the present invention provides a kind of composite cathode material for lithium ion cell and
Preparation method, especially a kind of Bi2Mn4O10/ Ketjen black-N composite cathode material for lithium ion cell and preparation method thereof, can have
Effect solves the problems such as current conventional transition metal oxide lithium ionic cell negative electrode material electric conductivity and poor cyclical stability；Section
The doping of Qin Hei-N can effectively improve Bi2Mn4O10The electric conductivity of material, wetability and Bi of the electrolyte to it2Mn4O10Material
The structural stability of material, to improve the chemical property of negative electrode material；The preparation method is simple, and cost is relatively low, environmental-friendly,
The development that can promote scale lithium ion battery negative material is expected to large-scale industrialization application.
To realize the above-mentioned technical purpose, the technical scheme of the present invention is realized as follows:
On the one hand, the present invention provides a kind of preparation method of composite cathode material for lithium ion cell, includes the following steps:
1) after mixing bismuth source, manganese source, solvent, through ball milling, calcining, Bi is made2Mn4O10Powder；
2) Ketjen black is placed in ammonia, calcines and Ketjen black (ECP)-N composite material is made；
3) by Bi2Mn4O10After powder and the mixing of Ketjen black (ECP)-N composite material, ball milling after solvent is added, obtains
Bi2Mn4O10/ Ketjen black (ECP)-N material precursor；
4) by Bi2Mn4O10/ Ketjen black-N material precursor, which is calcined, is made composite cathode material for lithium ion cell.
Further, the molar ratio of the bismuth source and manganese source is 1:2；The volume (mL) of the solvent: bismuth source and manganese source
Gross mass (g)=(1~2): 1.
Further, the manganese source is one or more of manganese acetate, manganese carbonate and manganese dioxide；The bismuth source is
One or more of bismuth oxalate, bismuth nitrate and bismuth subcarbonate.
Further, in step 1), time of the ball milling is 6~for 24 hours, preferably 12h, 18h, for 24 hours；Ball milling temperature is
Room temperature, preferably 15~35 DEG C.
Further, in step 1), the temperature of the calcining is 500~800 DEG C, preferably 500,600,800 DEG C.
Further, in step 1), the time of the calcining is 0.5~3h, preferably 0.5h, 1h, 3h.
Further, in step 2), the temperature of the calcining is 600~1000 DEG C, preferably 600,800,1000 DEG C.
Further, in step 2), the time of the calcining is 4~12h, preferably 6h, 8h, 10h.
Further, in step 3), time of the ball milling is 6~for 24 hours, preferably 10h, 12h, for 24 hours.
Further, in step 3), the Bi2Mn4O10Powder and Ketjen black/N composite material mass ratio are 100:
(0.01~0.1)；The volume (mL) of the solvent: Bi2Mn4O10Powder and Ketjen black/N composite material gross mass (g)=(1
~2): 1.
Further, in step 4), the temperature of the calcining is 300~400 DEG C, preferably 300,350,400 DEG C.
Further, in step 4), the time of the calcining is 0.5~3h, preferably 0.5h, 1h, 3h.
Further, the solvent is dehydrated alcohol.
Further, the partial size of the composite cathode material for lithium ion cell is 400~600nm.The lithium ion battery
Composite negative pole material pattern is granular.
On the one hand, the present invention provides a kind of composite cathode material for lithium ion cell, is prepared into accordance with the method for the present invention
It arrives.
On the other hand, the composite cathode material for lithium ion cell that the present invention provides a kind of above-mentioned preparation is preparing lithium-ion electric
Purposes in pond.
Beneficial effects of the present invention:
The present invention provides a kind of composite cathode material for lithium ion cell and preparation method thereof, and N is compounded in Ketjen black first
On, then by the Ketjen black and Bi of compound N2Mn4O10Powder is mixed, and solvent ball milling is added, obtains Bi2Mn4O10/ Ketjen black-
N material precursor；Composite material is can be obtained into presoma calcining, prepared material product purity is high, and partial size is small, to electrolysis
The wetability of liquid is good, and electric conductivity is strong.
Since the Ketjen black-N composite material of doping has good electric conductivity, the conductivity of material can be increased, reduced
The impedance of material is conducive to Bi of the invention2Mn4O10/ Ketjen black-N composite cathode material for lithium ion cell is in charge and discharge process
The raising of moderate multiplying factor performance；Meanwhile Ketjen black-N material is formed by carbon-coating (the visible TEM figure of carbon-coating), the body in process of intercalation
Product does not change substantially, simultaneously because its special layer structure, can effectively disperse in charge and discharge process suffered by material
Swelling stress is conducive to the raising of the stability of material.
Due to the doping of Ketjen black-N material, electrolyte is to Bi2Mn4O10/ Ketjen black-N lithium ion battery composite cathode material
The wetability of material enhances, and can further improve the cycle performance and high rate performance of material.
Bi prepared by the present invention2Mn4O10/ Ketjen black-N lithium ion battery composite material stable structure, conducts electricity very well, electricity
It is good to its wetability to solve liquid.There is excellent high rate performance and stable circulation performance, the ball as lithium ion battery negative material
Mill method can be carried out as long as at room temperature, and prepare conveniently, and low in cost, energy consumption is lower, easy to control, environmental-friendly, fit
Close lithium ion battery practical application and industrial-scale production.
Detailed description of the invention
It in order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, below will be to institute in embodiment
Attached drawing to be used is needed to be briefly described, it should be apparent that, the accompanying drawings in the following description is only some implementations of the invention
Example, for those of ordinary skill in the art, without creative efforts, can also obtain according to these attached drawings
Obtain other attached drawings.
Fig. 1 is 1 gained Bi of the embodiment of the present invention2Mn4O10The XRD diagram of/Ketjen black-N composite cathode material for lithium ion cell.
In figure, Bi2Mn4O10/ ECP-N is Bi2Mn4O10/ Ketjen black-N；JCPDS#27-0048 is Bi2Mn4O10The standard card of XRD spectrum
Piece；Intensity: intensity；Degree: degree.
Fig. 2 is 1 gained Bi of the embodiment of the present invention2Mn4O10SEM pairs of/Ketjen black-N composite cathode material for lithium ion cell
Than figure and TEM figure.(a)Bi2Mn4O10SEM picture (b) Bi of nano particle2Mn4O10The SEM picture (c) of/ECP-N composite material
Bi2Mn4O10The high definition transmission electron microscope picture of/ECP-N composite material, (d) the transmission electron microscope picture of Ketjen black.
Fig. 3 is 1 gained Bi of the embodiment of the present invention2Mn4O10The TEM- of/Ketjen black-N composite cathode material for lithium ion cell
MAPs figure.
Fig. 4 is 1 gained Bi of the embodiment of the present invention2Mn4O10/ Ketjen black-N composite cathode material for lithium ion cell cycle performance
Figure.
Fig. 5 is 1 gained Bi of the embodiment of the present invention2Mn4O10/ Ketjen black-N composite cathode material for lithium ion cell high rate performance
Figure.
Fig. 6 is 1 gained Bi of the embodiment of the present invention2Mn4O10/ Ketjen black (ECP)-N composite cathode material for lithium ion cell and
The electrolyte contacts angle comparison diagram of Ketjen black (ECP) and Ketjen black (ECP)-N.(a) Bi is coated2Mn4O10Material copper foil and electrolysis
Contact angle (b) coating Ketjen black (ECP) the material copper foil of liquid and the contact angle (c) of electrolyte coat Ketjen black (ECP)-N material
The contact angle of copper foil and electrolyte.
Specific embodiment
Following will be combined with the drawings in the embodiments of the present invention, and technical solution in the embodiment of the present invention carries out clear, complete
Site preparation description, it is clear that described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.It is based on
Embodiment in the present invention, those of ordinary skill in the art's every other embodiment obtained belong to what the present invention protected
Range.
Unless otherwise defined, all technical terms used hereinafter and the normally understood meaning of those skilled in the art
It is identical.Technical term used herein is intended merely to the purpose of description specific embodiment, is not intended to the limitation present invention
Protection scope.
Except there is a special instruction, the various reagents used in the present invention, raw material be can commodity commercially or
Person can the product as made from well known method.
Embodiment 1
Weigh the Bi of 0.025mol2(C2O4)3·7H2The MnCO of O and 0.1mol3, at room temperature with Bi:Mn=1:2 (mole
Than) stoichiometric ratio weigh after, be uniformly mixed.And it is L (ml) that liquid-solid ratio, which is added: M (g)=1:1 dehydrated alcohol is filled
It is put into the agate jar of 250mL after dividing mixing.After ball milling 18h, uniformly mixed presoma is obtained, is placed in Muffle furnace
It is calcined at 600 DEG C.Obtain Bi2Mn4O10Powder.
Ketjen black material is placed in NH3In, calcined under 800 DEG C of high temperature 6h obtain mixing N Ketjen black material (or are as follows:
Ketjen black/N composite material, similarly hereinafter).
By Bi2Mn4O10Powder and account for Bi2Mn4O10Powder quality is more uniform than Ketjen black/N composite material that score is 10%wt
Dehydrated alcohol is added, wherein the volume (mL) of dehydrated alcohol: Bi in mixing2Mn4O10Powder and the total matter of Ketjen black/N composite material
(g)=1:1 is measured, by dehydrated alcohol, Bi2Mn4O10Powder, Ketjen black/N composite material are put into togerther in 250mL agate jar
High-energy ball milling is carried out, obtains uniformly mixed Bi after 12h2Mn4O10/ Ketjen black-N material precursor, then by it in Muffle furnace
With 300 DEG C of temperature 1h, final product Bi is obtained2Mn4O10/ Ketjen black-N composite material.
The XRD diagram and TEM of the present embodiment products therefrom are schemed, by Fig. 1~3 it is found that the method using secondary wet process ball milling is closed
At Bi2Mn4O10/ Ketjen black-N composite material, the addition of Ketjen black material result in the widthization at the peak XRD, are not present in spectrogram
Impurity peaks, product purity are high.
The present invention uses secondary ball milling method to be prepared for Bi for the first time2Mn4O10/ Ketjen black-N composite material, and used for the first time
In lithium ion battery negative material, detailed process are as follows: by Bi2Mn4O10/ Ketjen black-N composite material, PVDF, acetylene black are according to matter
Amount mixes (gross mass 0.2000g) than the ratio for being 8:1:1, and N- methyl is added with rubber head dropper and adjoins pyrrolidone (NMP) dilution
Agent (25 drop), after mixing, it is uniformly coated on copper foil, the pole piece of 0.8cm × 0.8cm is cut into after drying, by lithium piece
Bi as reference electrode, with preparation2Mn4O10/ Ketjen black-N composite material pole piece is assembled into test cell together.
Charging/discharging voltage is set as 0.1-3.0V, discharge-rate 0.2C, preceding 100 enclose cycle performance, such as Fig. 4 and Fig. 5
Shown, after 100 circle of circulation, which is still able to maintain the capacity of 626.3mAh/g, under the multiplying power of 3C, is still able to maintain
The capacity of 284.7mAh/g has preferable circulating and reversible performance and high rate capability.
It will be appreciated from fig. 6 that coating Bi2Mn4O10The contact angle of material copper foil and electrolyte is 45.1 °；Coat Ketjen black material
The contact angle of copper foil and electrolyte is 2.34 °；The contact angle for coating Ketjen black-N material copper foil and electrolyte is 1.36 °.As it can be seen that
In Bi2Mn4O10After material doped Ketjen black-N, electrolyte will significantly improve its wetability.
Embodiment 2
Weigh the Bi of 0.025mol2(C2O4)3·7H2The MnCO of O and 0.1mol3, at room temperature with Bi:Mn=1:2 (mole
Than) stoichiometric ratio weigh after, be uniformly mixed.And it is L (ml): M (g)=2:1 dehydrated alcohol that liquid-solid ratio, which is added, then is carried out
It is put into after being sufficiently mixed in the agate jar of 250mL.After ball milling 12h, uniformly mixed presoma is obtained, Muffle furnace is placed in
It is interior to be calcined at 500 DEG C, obtain Bi2Mn4O10Powder.
Ketjen black material is placed in NH3In, the Ketjen black material that 12h obtains mixing N is calcined under 600 DEG C of high temperature.
By Bi2Mn4O10Powder and account for Bi2Mn4O10Powder quality is more uniform than Ketjen black/N composite material that score is 8%wt
Dehydrated alcohol is added, wherein the volume (mL) of dehydrated alcohol: Bi in mixing2Mn4O10Powder and the total matter of Ketjen black/N composite material
(g)=2:1 is measured, by dehydrated alcohol, Bi2Mn4O10Powder, Ketjen black/N composite material are put into togerther in 250mL agate jar
High-energy ball milling is carried out, obtains uniformly mixed Bi afterwards for 24 hours2Mn4O10/ Ketjen black-N material precursor, then by it in Muffle furnace
With 400 DEG C of temperature 0.5h, final product Bi is obtained2Mn4O10/ Ketjen black-N composite material.
The present embodiment has synthesized Bi using the method for secondary wet process ball milling2Mn4O10/ Ketjen black-N composite material, Ketjen black
Addition result in the widthization at the peak XRD, impurity peaks are not present in spectrogram, product purity is high.
The present invention uses secondary ball milling method to be prepared for Bi for the first time2Mn4O10/ Ketjen black-N composite material, and used for the first time
In lithium ion battery negative material, detailed process are as follows: by Bi2Mn4O10/ Ketjen black-N composite material, PVDF, acetylene black are according to matter
Amount mixes (gross mass 0.2000g) than the ratio for being 8:1:1, and N- methyl is added with rubber head dropper and adjoins pyrrolidone (NMP) dilution
Agent (25 drop), after mixing, it is uniformly coated on copper foil, the pole piece of 0.8cm × 0.8cm is cut into after the drying, by lithium
Bi of the piece as reference electrode, with preparation2Mn4O10/ Ketjen black-N composite material pole piece is assembled into test cell together.
Charging/discharging voltage is set as 0.1-3.0V, discharge-rate 0.2C is still able to maintain after circulation 100 is enclosed
The capacity of 491.3mAh/g has preferable circulating and reversible performance.
Embodiment 3
Weigh the Bi of 0.025mol2(C2O4)3·7H2The MnCO of O and 0.1mol3, at room temperature with Bi:Mn=1:2 (mole
Than) stoichiometric ratio weigh after, be uniformly mixed.And it is L (ml): M (g)=1.5:1 dehydrated alcohol that liquid-solid ratio, which is added, then into
Row is put into the agate jar of 250mL after being sufficiently mixed.Ball milling for 24 hours after, obtain uniformly mixed presoma, be placed in Muffle
It is calcined at 800 DEG C in furnace, obtains Bi2Mn4O10Powder.
Ketjen black material is placed in NH3In, the Ketjen black material that 4h obtains mixing N is calcined under 1000 DEG C of high temperature.
By Bi2Mn4O10Powder and account for Bi2Mn4O10Powder quality is more uniform than Ketjen black/N composite material that score is 6%wt
Dehydrated alcohol is added, wherein the volume (mL) of dehydrated alcohol: Bi in mixing2Mn4O10Powder and the total matter of Ketjen black/N composite material
(g)=1.5:1 is measured, by dehydrated alcohol, Bi2Mn4O10Powder, Ketjen black/N composite material are put into togerther 250mL agate jar
Interior carry out high-energy ball milling, obtains uniformly mixed Bi afterwards for 24 hours2Mn4O10/ Ketjen black-N material precursor, then by it in Muffle furnace
It is interior with 350 DEG C of temperature 3h, obtain final product Bi2Mn4O10/ Ketjen black-N composite material.
The present embodiment has synthesized Bi using the method for secondary wet process ball milling2Mn4O10/ Ketjen black-N composite material, Ketjen black
Addition result in the widthization at the peak XRD, impurity peaks are not present in spectrogram, product purity is high.
The present invention uses secondary ball milling method to be prepared for Bi for the first time2Mn4O10/ Ketjen black-N composite material, and used for the first time
In lithium ion battery negative material, detailed process are as follows: by Bi2Mn4O10/ Ketjen black-N composite material, PVDF, acetylene black are according to matter
Amount mixes (gross mass 0.2000g) than the ratio for being 8:1:1, and N- methyl is added with rubber head dropper and adjoins pyrrolidone (NMP) dilution
Agent (25 drop), after mixing, it is uniformly coated on copper foil, the pole piece of 0.8cm*0.8cm is cut into after the drying, by lithium piece
Bi as reference electrode, with preparation2Mn4O10/ Ketjen black-N composite material pole piece is assembled into test cell together.
Charging/discharging voltage is set as 0.1-3.0V, discharge-rate 0.2C still has 462.5mAh/g after circulation 100 is enclosed
Capacity has preferable circulating and reversible performance.
Embodiment 4
Weigh the Bi of 0.025mol2(C2O4)3·7H2The MnCO of O and 0.1mol3, at room temperature with Bi:Mn=1:2 (mole
Than) stoichiometric ratio weigh after, be uniformly mixed.And it is L (ml): M (g)=1:1 dehydrated alcohol that liquid-solid ratio, which is added, then is carried out
It is put into after being sufficiently mixed in the agate jar of 250mL.After ball milling 12h, uniformly mixed presoma is obtained, Muffle furnace is placed in
It is interior to be calcined at 600 DEG C, obtain Bi2Mn4O10Powder.
Ketjen black material is placed in NH3In, the Ketjen black material that 6h obtains mixing N is calcined under 800 DEG C of high temperature.
By Bi2Mn4O10Powder and account for Bi2Mn4O10Powder quality is more uniform than Ketjen black/N composite material that score is 4%wt
Dehydrated alcohol is added, wherein the volume (mL) of dehydrated alcohol: Bi in mixing2Mn4O10Powder and the total matter of Ketjen black/N composite material
(g)=2:1 is measured, by dehydrated alcohol, Bi2Mn4O10Powder, Ketjen black/N composite material are put into togerther in 250mL agate jar
High-energy ball milling is carried out, obtains uniformly mixed Bi after 10h2Mn4O10/ Ketjen black-N material precursor, then by it in Muffle furnace
With 400 DEG C of temperature 3h, final product Bi is obtained2Mn4O10/ Ketjen black-N composite material.
The present embodiment has synthesized Bi using the method for secondary wet process ball milling2Mn4O10/ Ketjen black-N composite material, Ketjen black
Addition result in the widthization at the peak XRD, impurity peaks are not present in spectrogram, product purity is high.
The present invention uses secondary ball milling method to be prepared for Bi for the first time2Mn4O10/ Ketjen black-N composite material, and used for the first time
In lithium ion battery negative material, detailed process are as follows: by Bi2Mn4O10/ Ketjen black-N composite material, PVDF, acetylene black are according to matter
Amount mixes (gross mass 0.2000g) than the ratio for being 8:1:1, and N- methyl is added with rubber head dropper and adjoins pyrrolidone (NMP) dilution
Agent (25 drop), after mixing, it is uniformly coated on copper foil, the pole piece of 0.8cm*0.8cm is cut into after drying, lithium piece is made
Bi for reference electrode, with preparation2Mn4O10/ Ketjen black-N composite material pole piece is assembled into test cell together.
Charging/discharging voltage is set as 0.1-3.0V, discharge-rate 0.2C still has 451.7mAh/g after circulation 100 is enclosed
Capacity, have preferable circulating and reversible performance.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Within mind and principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.
Claims (10)
1. a kind of preparation method of composite cathode material for lithium ion cell, which comprises the steps of:
1) after mixing bismuth source, manganese source, solvent, through ball milling, calcining, Bi is made2Mn4O10Powder；
2) Ketjen black is placed in ammonia, calcines and Ketjen black-N composite material is made；
3) by Bi2Mn4O10After powder and the mixing of Ketjen black-N composite material, solvent is added, obtains Bi through ball milling2Mn4O10/ section qin
Black-N material precursor；
4) by Bi2Mn4O10/ Ketjen black-N material precursor, which is calcined, is made composite cathode material for lithium ion cell.
2. the preparation method of composite cathode material for lithium ion cell according to claim 1, which is characterized in that the bismuth source
Molar ratio with manganese source is 1:2；The volume (mL) of solvent: the gross mass (g) of bismuth source and manganese source=(1~2): 1.
3. the preparation method of composite cathode material for lithium ion cell according to claim 1, which is characterized in that the manganese source
For one or more of manganese acetate, manganese carbonate and manganese dioxide；The bismuth source is bismuth oxalate, bismuth nitrate and bismuth subcarbonate
One or more of；The solvent is dehydrated alcohol.
4. the preparation method of composite cathode material for lithium ion cell according to claim 1, which is characterized in that step 1)
In, time of the ball milling is 6~for 24 hours, ball milling temperature is room temperature；
The temperature of the calcining is 500~800 DEG C, and the time of the calcining is 0.5~3h.
5. the preparation method of composite cathode material for lithium ion cell according to claim 1, which is characterized in that step 2)
In, the temperature of the calcining is 600~1000 DEG C, and the time of the calcining is 4~12h.
6. the preparation method of composite cathode material for lithium ion cell according to claim 1, which is characterized in that step 3)
In, time of the ball milling is 6~for 24 hours, the Bi2Mn4O10The mass ratio of powder and Ketjen black-N composite material is 100:
(0.01~0.1)；The volume (L) of solvent: Bi2Mn4O10Powder and Ketjen black/N composite material gross mass (g)=(1~2):
1。
7. the preparation method of composite cathode material for lithium ion cell according to claim 1, which is characterized in that step 4)
In, the temperature of the calcining is 300~400 DEG C, and the time of the calcining is 0.5~3h.
8. the preparation method of composite cathode material for lithium ion cell according to claim 1, which is characterized in that the lithium from
The partial size of sub- battery composite cathode material is 400~600nm.
9. a kind of composite cathode material for lithium ion cell, which is characterized in that any method system according to claim 1~8
It is standby to obtain.
10. a kind of composite cathode material for lithium ion cell of any the method preparation of claim 1~8 is preparing lithium-ion electric
Purposes in pond.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104528833A (en) * | 2014-12-12 | 2015-04-22 | 江苏大学 | Preparation method of metal oxide/nitrogen doped graphene composite material |
| CN106328910A (en) * | 2016-11-22 | 2017-01-11 | 南阳师范学院 | Spherical nitrogen-doped carbon material and transition metal oxide composite and preparation method thereof |
| WO2017197675A1 (en) * | 2016-05-20 | 2017-11-23 | 山东玉皇新能源科技有限公司 | Lithium titanate-modified material and manufacturing method thereof |
| CN107935049A (en) * | 2017-11-02 | 2018-04-20 | 中南大学 | A kind of lithium ion battery negative material Bi2Mn4O10Preparation and its application |
-
2018
- 2018-11-27 CN CN201811421018.3A patent/CN109378463A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104528833A (en) * | 2014-12-12 | 2015-04-22 | 江苏大学 | Preparation method of metal oxide/nitrogen doped graphene composite material |
| WO2017197675A1 (en) * | 2016-05-20 | 2017-11-23 | 山东玉皇新能源科技有限公司 | Lithium titanate-modified material and manufacturing method thereof |
| CN106328910A (en) * | 2016-11-22 | 2017-01-11 | 南阳师范学院 | Spherical nitrogen-doped carbon material and transition metal oxide composite and preparation method thereof |
| CN107935049A (en) * | 2017-11-02 | 2018-04-20 | 中南大学 | A kind of lithium ion battery negative material Bi2Mn4O10Preparation and its application |
Non-Patent Citations (1)
| Title |
|---|
| ZIHAN SONG 等: "Bi2Mn4O10: a new mullite-type anode material for lithium-ion batteries", 《DALTON TRANSACTIONS》 * |
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