CN108807886A - Double-coating anode material for lithium-ion batteries LiNi0.6Co0.2Mn0.2O2And preparation method thereof - Google Patents

Double-coating anode material for lithium-ion batteries LiNi0.6Co0.2Mn0.2O2And preparation method thereof Download PDF

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CN108807886A
CN108807886A CN201810552591.1A CN201810552591A CN108807886A CN 108807886 A CN108807886 A CN 108807886A CN 201810552591 A CN201810552591 A CN 201810552591A CN 108807886 A CN108807886 A CN 108807886A
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lithium
lini
ppy
ion batteries
anode material
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刘兴泉
冉淇文
张美玲
胡友作
刘金涛
谭明
刘珊珊
舒小会
李�浩
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University of Electronic Science and Technology of China
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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
    • 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
    • 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
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention belongs to the preparing technical fields of anode material for lithium-ion batteries, specific to provide double-coating anode material for lithium-ion batteries LiNi0.6Co0.2Mn0.2O2, wherein Li3VO4Covering amount with PPy is 1~5wt%；Li3VO4It is a kind of lithium fast-ionic conductor, coats Li3VO4Protective layer can be not only provided, but also lithium fast-ionic conductor can be provided, coat Li3VO4Protective layer can be not only provided, but also lithium fast-ionic conductor can be provided, the ionic conductivity of reinforcing material, and the lithium ion consumed when the formation of SEI and CEI films is made up, improve the cycle performance of material；PPy is a kind of fast electronic conductive material, and cladding PPy can not only provide the second protective layer, but also can improve the electron conduction of material.Li3VO4With the double-coating of PPy, both ionic conductivity is improved, improve electron conduction again simultaneously, this not only makes the positive electrode be provided with the multiplying power discharging property of superelevation, and the positive electrode is made to be provided with higher specific discharge capacity, two-coat more efficient can also inhibit corrosion functions of the HF to positive electrode, and the positive electrode is made to be provided with excellent high voltage cycle stability.

Description

Double-coating anode material for lithium-ion batteries LiNi0.6Co0.2Mn0.2O2And its it prepares Method
Technical field
The invention belongs to the preparing technical fields of anode material for lithium-ion batteries, and in particular to a kind of lithium ion cell positive Material and preparation method thereof, the positive electrode have following chemical formula LiNi0.6Co0.2Mn0.2O2@Li3VO4@PPy, wherein coating Li3VO4The quality of@PPy is respectively fertile material LiNi0.6Co0.2Mn0.2O21~5wt% (mass ratio).
Background technology
It is environmental-friendly as the problems such as traditional fossil energy is deficient and environmental pollution, climate warming increasingly sharpens New energy source technology is also at one of the hot spot of current development and application；Wherein, lithium ion battery by feat of it with high energy The features such as metric density, smaller self discharge, excellent cycle performance and memory-less effect, becomes new-energy automobile production instantly The vital part in power battery field in industry.
Lithium ion battery is mainly made of positive electrode, negative material, diaphragm and electrolyte.Lithium ion cell positive at present Material can realize industrialized mainly have：Cobalt acid lithium, LiMn2O4, LiFePO4 and tertiary cathode material (NCM, NCA).Ternary is just Pole material is the positive electrode for most having in power lithium-ion battery positive electrode instantly the market competitiveness, tertiary cathode material The trielement synergistic effect of structural stability formation of the NCM by improving the content of Ni and by Co and Mn, to be carried in capacity Reduce the influence to the cyclical stability of material while liter；In order to meet demand of the market to positive electrode energy density, Nickelic (Ni >=0.6) direction of tertiary cathode material forward direction is developed.In the application process of practical commercial, in order to realize that energy is close Degree further increases, and to tertiary cathode material, by voltage, more stringent requirements are proposed, but electrolyte under high voltages Aggravation is decomposed, the HF of generation, which can dissolve transition metal ions, leads to the structure collapses of positive electrode, the cycle of tertiary cathode material Stability drastically declines, and safety is also challenged.
Invention content
It is an object of the invention to be directed to the nickelic nickle cobalt lithium manganate of anode material for lithium-ion batteries stratiform LiNi0.6Co0.2Mn0.2O2Under high voltages the shortcomings that poor circulation, a kind of lithium-ion electric of surface double coating modification is provided Pond positive electrode LiNi0.6Co0.2Mn0.2O2@Li3VO4@PPy, wherein Li3VO4Covering amount with PPy is 3wt%；Li3VO4 It is a kind of lithium fast-ionic conductor, coats Li3VO4Protective layer can be not only provided, but also lithium fast-ionic conductor can be provided, enhanced The ionic conductivity of material, and make up the lithium ion consumed when the formation of SEI and CEI films；PPy is a kind of fast electronic conductive material, Cladding PPy can not only provide the second protective layer, but also can improve the electron conduction of material, and the high magnification for improving material is put Electrical property.Li3VO4With the double-coating of PPy, ionic conductivity is not only improved, but also improve electron conduction, this is not only So that the positive electrode is provided with the multiplying power discharging property of superelevation, and the positive electrode made to be provided with higher specific discharge capacity, Two-coat more efficient can also inhibit corrosion functions of the HF to positive electrode, and the positive electrode is made to be provided with excellent high voltage Stable circulation performance.The present invention not only substantially increases LiNi0.6Co0.2Mn0.2O2Energy density, and make parent anode material Expect LiNi0.6Co0.2Mn0.2O2Has the ability of trouble free service under high voltages.
To achieve the above object, the technical solution adopted by the present invention is：
A kind of anode material for lithium-ion batteries LiNi0.6Co0.2Mn0.2O2@Li3VO4@PPy, which is characterized in that the lithium The chemical expression of ion battery positive electrode is：LiNi0.6Co0.2Mn0.2O2@Li3VO4@PPy, wherein Li3VO4With PPy to mother Body material LiNi0.6Co0.2Mn0.2O2Double-coating is carried out, covering amount is 1~5wt% of fertile material.
A kind of anode material for lithium-ion batteries LiNi0.6Co0.2Mn0.2O2@Li3VO4The preparation method of@PPy, feature exist In including the following steps：
Step 1. is by lithium source and V2O5In molar ratio 6:1 is dissolved in deionized water, and puts and be stirred at room temperature, and is mixed Close liquid A；
Citric acid is dissolved in appropriate amount of deionized water by step 2., according still further to n (citric acid):N (fertile material)=1:1 adds Enter fertile material LiNi0.6Co0.2Mn0.2O2, mixed liquid B is obtained after stirring evenly, and mixed liquid B is then added to mixed liquor A In, stirring in water bath, obtains mixed liquor C at room temperature；
Ammonium hydroxide is added dropwise into step 2 gained mixed liquor C for step 3., and it is 6~8 to adjust pH value, is warming up to 50~80 DEG C of water-baths Stirring is until form wet gel；
Step 3 gained wet gel is put in air dry oven by step 4., and dry 10~20h is obtained at 80~120 DEG C Xerogel；
Step 4 gained xerogel is placed in tube furnace and is warming up to 500 under oxygen atmosphere with 2~5 DEG C/min by step 5. ~900 DEG C are sintered 5~10h, then after Temperature fall that product is levigate, are prepared into the anode material for lithium-ion batteries of layer structure LiNi0.6Co0.2Mn0.2O2@Li3VO4, wherein Li3VO4Covering amount is 1~5wt%；
Step 6. is by paratoluenesulfonic acid sodium salt and pyrrole monomer in molar ratio 1:3 are dissolved in absolute ethyl alcohol, and are placed on room temperature Lower stirring, obtains mixed liquor D；
Step 7. is with LiNi0.6Co0.2Mn0.2O2@Li3VO4For parent stock, it is added into mixed liquor D and is sufficiently stirred, obtain To mixed liquor E；
Step 8. pyrrole monomer in molar ratio：FeCl3·6H2O=1：1 by FeCl3·6H2O is dissolved in absolute ethyl alcohol, Then it is added dropwise in mixed liquor E and is placed in 3~6h of stirring under ice bath, obtain mixed liquor F；
Mixed liquor F is filtered, is washed until filtrate is colourless by step 9., then will be deposited at 60-80 DEG C It is dried in vacuo 8-12h, obtains LiNi0.6Co0.2Mn0.2O2@Li3VO4@PPy positive electrodes, wherein PPy covering amounts are still parent material Expect LiNi0.6Co0.2Mn0.2O21~5wt%.
Further, the fertile material LiNi0.6Co0.2Mn0.2O2Preparation process be：
First, by lithium source and presoma Ni0.6Co0.2Mn0.2(OH)2(1~1.1) in molar ratio:1 mixed grinding, with alcohol For dispersant, grinding is uniform and dries, and obtains mixture；
Then, gained mixture is first warming up to 500 DEG C of pre-burnings under oxygen atmosphere in tube furnace with 3-5 DEG C/min 6h, then 800~950 DEG C of roasting 15-24h are warming up to 2-3 DEG C/min, it is product is levigate after Temperature fall, it is made LiNi0.6Co0.2Mn0.2O2。
The lithium source raw material is at least one of lithium carbonate, lithium nitrate, lithium acetate, lithium chloride and lithium hydroxide.
The lithium source raw material, V2O5Specific metering Li in mass ratio3VO4：LiNi0.6Co0.2Mn0.2O2=1~5：100 (i.e. 1~5wt% mass ratioes) metering than calculate.
The present invention is by lithium fast-ionic conductor Li3VO4It is combined with fast electronic conductor PPy, utilizes Li3VO4Ionic conductivity Surface coating modification carried out respectively to NCM622 with the electron conduction of PPy, modified positive electrode not only have it is high from Subconductivity, it may have high electron conduction, moreover it is possible to inhibit HF to the corrosion function of positive electrode to promote the cycle of material Performance.Compared to traditional NCM622 positive electrodes, LiNi0.6Co0.2Mn0.2O2@Li3VO4@PPy positive electrodes can be in high electricity Pressure discharges more lithium ions, while the stability of holding structure.
In conclusion the beneficial effects of the present invention are：
1, LiNi prepared by the present invention0.6Co0.2Mn0.2O2@Li3VO4@PPy layered lithium ion battery positive electrodes, pass through by Lithium fast-ionic conductor Li3VO4It is combined with fast electronic conductor PPy, promotes the ionic conductivity and electron conduction of positive electrode, Chemical property of the positive electrode under high magnification is set to be significantly improved.Coat Li3VO4Protective layer can be not only provided, and And lithium fast-ionic conductor can be provided, the ionic conductivity of reinforcing material, and can overcome the disadvantages that the lithium consumed when the formation of SEI and CEI films Ion, the cycle performance of modified material；
2, LiNi prepared by the present invention0.6Co0.2Mn0.2O2@Li3VO4@PPy layered lithium ion battery positive electrodes, by right The surface cladding processing of fertile material, can inhibit the HF of electrolyte decomposition under high voltage to the dissolving of transition metal ions to Greatly promote the stable circulation performance of material.
3, the present invention can develop more obvious layer using traditional high temperature solid-state method by grinding for a long time Shape structure；Cladding uses sol-gal process technique, and metal ion is fixed by organic complexing agent, and reaction raw materials mixing is equal Even, the shortcomings that overcoming Traditional liquid phase synthetic method, the clad chemical uniformity of preparation is good and the thickness control of clad is several The electrochemical impedance of material is greatly reduced in the range of nanometer.
4, anode material for lithium-ion batteries LiNi prepared by the present invention0.6Co0.2Mn0.2O2@Li3VO4@PPy have higher Specific discharge capacity and excellent cycle performance；Under room temperature environment, when voltage range is in 2.7~4.5V, constant current charge-discharge times When rate is 0.5C (1C=180mA/g), the first discharge specific capacity of the anode material for lithium-ion batteries can reach 203.6mAh g-1, still can reach 174.0mAh g after recycling 100 times-1, capacity retention ratio 85.4%.Constant current charge-discharge multiplying power is 5C When (1C=180mA/g), the first discharge specific capacity of the anode material for lithium-ion batteries can reach 137.5mAh g-1, cycle 100 121.7mAh g are still can reach after secondary-1, capacity retention ratio 88.5%；
5, generated without poisonous and harmful substance in preparation process of the invention, in environmental-friendly and technique involved production set It is standby simple, it is relatively easy to realize scale industrial production.
Description of the drawings
Fig. 1 is that the present invention prepares anode material for lithium-ion batteries LiNi0.6Co0.2Mn0.2O2@Li3VO4The technological process of@PPy Figure.
Fig. 2 is that the present invention prepares anode material for lithium-ion batteries LiNi0.6Co0.2Mn0.2O2Process flow chart.
Fig. 3 is that the present invention prepares anode material for lithium-ion batteries LiNi0.6Co0.2Mn0.2O2@Li3VO4Process flow chart.
Fig. 4 is that the embodiment of the present invention 1 prepares anode material for lithium-ion batteries LiNi0.6Co0.2Mn0.2O2@Li3VO4@PPy's XRD diagram.
Fig. 5 is that the embodiment of the present invention 1 prepares anode material for lithium-ion batteries LiNi0.6Co0.2Mn0.2O2@Li3VO4@PPy's SEM schemes.
Fig. 6 is that the embodiment of the present invention 1 prepares anode material for lithium-ion batteries LiNi0.6Co0.2Mn0.2O2@Li3VO4@PPy's EDX Mapping figures.
Fig. 7 is that the embodiment of the present invention 1 prepares different anode material for lithium-ion batteries in 2.7~4.5 voltage ranges, with 0.5C (1C=180mA/g) rate charge-discharge cycle performance curve graph.
Fig. 8 is that the embodiment of the present invention 1 prepares anode material for lithium-ion batteries in 2.7~4.5V voltage ranges, with 5C (1C =180mA/g) rate charge-discharge cycle performance curve graph.
Specific implementation mode
With reference to specific embodiment, the present invention is described in further detail with attached drawing.
Embodiment 1
The present embodiment provides anode material for lithium-ion batteries LiNi0.6Co0.2Mn0.2O2@Li3VO4@PPy, wherein Li3VO4With PPy is to fertile material LiNi0.6Co0.2Mn0.2O2Dual cladding is carried out, covering amount is fertile material LiNi0.6Co0.2Mn0.2O2's 3wt%；Its preparation process is as follows：
The LiOHH of 0.42mol is weighed by excessive 5% molar ratio of lithium source2O, that is, 17.623g weighs presoma 36.801g And mix, it using absolute ethyl alcohol as dispersant, is fully ground uniformly mixed, then is placed in air dry oven and is completely dried and fully grinds Mill, is finally placed in tube furnace that (oxygen gas flow rate 400ml/min) is warming up to the speed of 3 DEG C/min under the atmosphere of oxygen Then 500 DEG C of heat preservation 6h are warming up to 820 DEG C of heat preservation 15h with the speed of 2 DEG C/min again, are naturally cooling to 100 DEG C, take out abundant Grinding is to get to LiNi0.6Co0.2Mn0.2O2Parent positive electrode (fertile material)；As shown in Figure 2.
When covering amount is the 3wt% of fertile material, ratio is measured by exact chemical, weighs the LiNi of 5g0.6Co0.2Mn0.2O2 Positive electrode (fertile material), weighs the LiOHH of 0.1388g2The V of O and 0.1003g2O5It is dissolved in deionized water, marks It is denoted as mixing A liquid；The citric acid of 0.64g is dissolved in appropriate amount of deionized water, then the fertile material of 5g is added thereto, is stirred Uniformly, it is labeled as mixing B liquid, is then slowly added in mixing A liquid, at room temperature stirring in water bath, mixing C liquid is obtained；To mixed It closes and ammonium hydroxide is added dropwise in C liquid, it is 6~8 to adjust pH value, is warming up to 80 DEG C of stirring in water bath until forming wet gel；By gained wet gel It is put in air dry oven, dry 12h obtains xerogel at 80~120 DEG C；By gained xerogel be positioned in tube furnace in 700 DEG C of sintering 8h are warming up to 2 DEG C/min under oxygen atmosphere, it is product is levigate after Temperature fall, you can layer structure is made Anode material for lithium-ion batteries LiNi0.6Co0.2Mn0.2O2@Li3VO4(being denoted as parent stock)；As shown in Figure 3.
By paratoluenesulfonic acid sodium salt and pyrrole monomer in molar ratio 1：3 are dissolved in appropriate absolute ethyl alcohol, and are placed at room temperature Stirring obtains mixing D liquid；After parent stock addition mixing D liquid is sufficiently stirred, and labeled as mixing E liquid；By FeCl3·6H2O (pyrrole monomer in molar ratio：FeCl3·6H2O=1：1) it is dissolved in appropriate absolute ethyl alcohol, mixing E liquid is then added dropwise simultaneously It is positioned under ice bath and stirs 6h, obtain mixing F liquid；Mixing F liquid is filtered, is washed, until filtrate is colourless, then It will be deposited at 60 DEG C and be dried in vacuo 12h to get to LiNi0.6Co0.2Mn0.2O2@Li3VO4@PPy positive electrodes；As shown in Figure 1.
To the anode material for lithium-ion batteries LiNi of preparation0.6Co0.2Mn0.2O2@Li3VO4@PPy carry out constant current charge-discharge Test, result as shown in Fig. 4~Fig. 8, from test result it can be seen that the positive electrode have higher specific discharge capacity and Preferable stable circulation performance；Under room temperature environment, when voltage range is in 2.7~4.5V, constant current charge-discharge multiplying power is 0.5C When (1C=180mA/g), the first discharge specific capacity of the anode material for lithium-ion batteries can reach 203.6mAh g-1, cycle 100 174.0mAh g are still can reach after secondary-1, capacity retention ratio 85.4%；When voltage range is in 2.7~4.5V, constant current charge and discharge When electric multiplying power is 5C (1C=180mA/g), the initial discharge specific capacity of the anode material for lithium-ion batteries can reach 137.5mAh g-1, still can reach 121.7mAh g after recycling 100 times-1, capacity retention ratio is up to 88.5%.
The above description is merely a specific embodiment, any feature disclosed in this specification, except non-specifically Narration, can be replaced by other alternative features that are equivalent or have similar purpose；Disclosed all features or all sides Method or in the process the step of, other than mutually exclusive feature and/or step, can be combined in any way.

Claims (5)

1. double-coating anode material for lithium-ion batteries LiNi0.6Co0.2Mn0.2O2, which is characterized in that the lithium ion battery is just The chemical expression of pole material is：LiNi0.6Co0.2Mn0.2O2@Li3VO4@PPy, wherein Li3VO4With PPy to fertile material LiNi0.6Co0.2Mn0.2O2Double-coating is carried out, covering amount is 1~5wt% of fertile material.
2. double-coating anode material for lithium-ion batteries LiNi0.6Co0.2Mn0.2O2Preparation method, which is characterized in that including following Step：
Step 1. is by lithium source and V2O5In molar ratio 6:1 is dissolved in deionized water, and puts and be stirred at room temperature, and obtains mixed liquor A；
Citric acid is dissolved in appropriate amount of deionized water by step 2., according still further to n (citric acid):N (fertile material)=1:1 is added mother Body material LiNi0.6Co0.2Mn0.2O2, mixed liquid B is obtained after stirring evenly, and then mixed liquid B is added in mixed liquor A, Stirring in water bath at room temperature obtains mixed liquor C；
Ammonium hydroxide is added dropwise into step 2 gained mixed liquor C for step 3., and it is 6~8 to adjust pH value, is warming up to 50~80 DEG C of stirring in water bath Until forming wet gel；
Step 3 gained wet gel is put in air dry oven by step 4., and dry 10~20h obtains dry solidifying at 80~120 DEG C Glue；
Step 4 gained xerogel is placed in tube furnace and is warming up to 500~900 under oxygen atmosphere with 2~5 DEG C/min by step 5. DEG C sintering 5~10h, it is then after Temperature fall that product is levigate, be prepared into the anode material for lithium-ion batteries of layer structure LiNi0.6Co0.2Mn0.2O2@Li3VO4, wherein Li3VO4Covering amount is 1~5wt%；
Step 6. is by paratoluenesulfonic acid sodium salt and pyrrole monomer in molar ratio 1:3 are dissolved in absolute ethyl alcohol, and are placed on and stir at room temperature It mixes, obtains mixed liquor D；
Step 7. is with LiNi0.6Co0.2Mn0.2O2@Li3VO4For parent stock, it is added into mixed liquor D and is sufficiently stirred, mixed Close liquid E；
Step 8. pyrrole monomer in molar ratio：FeCl3·6H2O=1：1 by FeCl3·6H2O is dissolved in absolute ethyl alcohol, then by It is added dropwise in mixed liquor E and is placed in 3~6h of stirring under ice bath, obtain mixed liquor F；
Mixed liquor F is filtered, is washed until filtrate is colourless by step 9., then will be deposited in vacuum at 60-80 DEG C Dry 8-12h, obtains LiNi0.6Co0.2Mn0.2O2@Li3VO4@PPy positive electrodes, wherein PPy covering amounts are still fertile material LiNi0.6Co0.2Mn0.2O21~5wt%.
3. by double-coating anode material for lithium-ion batteries LiNi described in claim 20.6Co0.2Mn0.2O2Preparation method, it is special Sign is, the fertile material LiNi0.6Co0.2Mn0.2O2Preparation process be：
First, by lithium source and presoma Ni0.6Co0.2Mn0.2(OH)2(1~1.1) in molar ratio:1 mixed grinding is point with alcohol Powder, grinding is uniform and dries, and obtains mixture；
Then, gained mixture is first warming up to 500 DEG C of pre-burning 6h under oxygen atmosphere in tube furnace with 3-5 DEG C/min, then 800~950 DEG C of roasting 15-24h are warming up to 2-3 DEG C/min, it is product is levigate after Temperature fall, it is made LiNi0.6Co0.2Mn0.2O2。
4. by anode material for lithium-ion batteries LiNi described in claim 20.6Co0.2Mn0.2O2@Li3VO4The preparation method of@PPy, It is characterized in that, the lithium source raw material is at least one of lithium carbonate, lithium nitrate, lithium acetate, lithium chloride and lithium hydroxide.
5. by double-coating anode material for lithium-ion batteries LiNi described in claim 20.6Co0.2Mn0.2O2Preparation method, it is special Sign is, the lithium source raw material, V2O5Specific metering Li in mass ratio3VO4：LiNi0.6Co0.2Mn0.2O2=1~5：100 (i.e. 1 ~5wt% mass ratioes) metering than calculate.
CN201810552591.1A 2018-05-31 2018-05-31 Double-coating anode material for lithium-ion batteries LiNi0.6Co0.2Mn0.2O2And preparation method thereof Pending CN108807886A (en)

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Cited By (11)

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CN109616627A (en) * 2018-11-16 2019-04-12 宁波容百新能源科技股份有限公司 A kind of high safety, height ratio capacity, nickelic positive electrode and preparation method thereof and a kind of lithium ion battery
CN109888252A (en) * 2019-03-29 2019-06-14 荆门市格林美新材料有限公司 It is a kind of to coat nickel-cobalt-manganese ternary anode material and preparation method altogether
CN111326709A (en) * 2018-12-14 2020-06-23 大众汽车有限公司 Electrode active material with coating in multilayer system and lithium ion battery cell
CN111969189A (en) * 2020-08-21 2020-11-20 贵州梅岭电源有限公司 Lithium ion battery composite negative electrode material and preparation method thereof
CN112002897A (en) * 2020-08-12 2020-11-27 中南大学 Dual-modified lithium ion battery positive electrode material and preparation method thereof
CN112349905A (en) * 2019-08-06 2021-02-09 湖南杉杉新能源有限公司 Double-coating modified lithium ion battery positive electrode material and preparation method thereof
CN112542583A (en) * 2019-09-23 2021-03-23 珠海冠宇电池股份有限公司 Positive electrode active material and high-voltage lithium ion battery comprising same
CN113471415A (en) * 2020-03-31 2021-10-01 北京卫蓝新能源科技有限公司 Composite coated lithium ion battery anode material and preparation method thereof
CN113471414A (en) * 2020-03-31 2021-10-01 北京卫蓝新能源科技有限公司 Lithium ion battery composite positive electrode material and preparation method and application thereof
CN114079053A (en) * 2021-11-23 2022-02-22 蜂巢能源科技有限公司 Cathode material with composite coating layer and preparation method thereof
CN114388759A (en) * 2022-01-13 2022-04-22 厦门大学 Double-coated composite material and preparation method and application thereof

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CN102531057A (en) * 2012-01-17 2012-07-04 重庆市科学技术研究院 Method for preparing lithium vanadate as cathode material of lithium ion battery
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Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109616627A (en) * 2018-11-16 2019-04-12 宁波容百新能源科技股份有限公司 A kind of high safety, height ratio capacity, nickelic positive electrode and preparation method thereof and a kind of lithium ion battery
CN111326709A (en) * 2018-12-14 2020-06-23 大众汽车有限公司 Electrode active material with coating in multilayer system and lithium ion battery cell
CN109888252A (en) * 2019-03-29 2019-06-14 荆门市格林美新材料有限公司 It is a kind of to coat nickel-cobalt-manganese ternary anode material and preparation method altogether
CN109888252B (en) * 2019-03-29 2021-12-07 荆门市格林美新材料有限公司 Co-coated nickel-cobalt-manganese ternary positive electrode material and preparation method thereof
CN112349905B (en) * 2019-08-06 2021-11-23 湖南杉杉新能源有限公司 Double-coating modified lithium ion battery positive electrode material and preparation method thereof
CN112349905A (en) * 2019-08-06 2021-02-09 湖南杉杉新能源有限公司 Double-coating modified lithium ion battery positive electrode material and preparation method thereof
WO2021023313A1 (en) * 2019-08-06 2021-02-11 湖南杉杉新能源有限公司 Lithium-ion battery anode material modified using dual coating layers, and preparation method therefor
CN112542583A (en) * 2019-09-23 2021-03-23 珠海冠宇电池股份有限公司 Positive electrode active material and high-voltage lithium ion battery comprising same
CN113471414A (en) * 2020-03-31 2021-10-01 北京卫蓝新能源科技有限公司 Lithium ion battery composite positive electrode material and preparation method and application thereof
CN113471415A (en) * 2020-03-31 2021-10-01 北京卫蓝新能源科技有限公司 Composite coated lithium ion battery anode material and preparation method thereof
CN112002897A (en) * 2020-08-12 2020-11-27 中南大学 Dual-modified lithium ion battery positive electrode material and preparation method thereof
CN111969189B (en) * 2020-08-21 2021-10-26 贵州梅岭电源有限公司 Lithium ion battery composite negative electrode material and preparation method thereof
CN111969189A (en) * 2020-08-21 2020-11-20 贵州梅岭电源有限公司 Lithium ion battery composite negative electrode material and preparation method thereof
CN114079053A (en) * 2021-11-23 2022-02-22 蜂巢能源科技有限公司 Cathode material with composite coating layer and preparation method thereof
CN114388759A (en) * 2022-01-13 2022-04-22 厦门大学 Double-coated composite material and preparation method and application thereof

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Application publication date: 20181113