CN107799739A - A kind of nickel cobalt manganese anode material for lithium-ion batteries of vanadium doping - Google Patents
A kind of nickel cobalt manganese anode material for lithium-ion batteries of vanadium doping Download PDFInfo
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- CN107799739A CN107799739A CN201710892818.2A CN201710892818A CN107799739A CN 107799739 A CN107799739 A CN 107799739A CN 201710892818 A CN201710892818 A CN 201710892818A CN 107799739 A CN107799739 A CN 107799739A
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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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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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
- H01M4/50—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
- H01M4/36—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
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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
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses nickel cobalt manganese anode material for lithium-ion batteries of a kind of vanadium doping and preparation method thereof, the chemical expression of the nickel cobalt manganese anode material for lithium-ion batteries of vanadium doping is LiaNixCoyMnzVbO2, wherein 1≤a≤1.2；0.3≤x≤0.98；0.01≤y≤0.6；0.001≤z≤0.6；B=4/5 a/5 3x/5 3y/5 3z/5,0.00001≤b≤0.2.The present invention by the compound of monocrystalline nickel cobalt manganese composite precursor and vanadium by carrying out ultrahigh speed premixing, again by the compound of monocrystalline nickel cobalt manganese presoma and vfanadium compound and common polycrystalline nickel cobalt manganese presoma mixed at high speed, improve mixed effect, because monocrystalline composite precursor high mechanical strength, ultra-high-speed mixing can be used, and is unlikely to broken, while monocrystalline composite precursor can play a part of collision medium, the compound of vanadium is fully broken up, is sufficiently mixed doped chemical and host element.
Description
Technical field
The invention belongs to battery material technical field, and in particular to a kind of nickel cobalt manganese lithium ion cell positive material of vanadium doping
Material and preparation method thereof.
Background technology
Nickel cobalt manganese lithium (LNCA) ion battery positive electrode is due to very high energy density and relatively low valency
Lattice are widely used in IT product and new-energy automobile field, but simple nickle cobalt lithium manganate belongs to semi-conducting material, electronics
Electrical conductivity is very low；And the conduction of lithium ion is also very big by the resistance of transmission channel, its electrical conductivity is caused there was only 10-9-10-7S/cm；And the electrical conductivity of positive electrode directly affects the charging interval of IT product battery and the big multiplying power discharging of electrokinetic cell
Performance, as to the higher and higher requirement of lithium ion battery fast charging and discharging, the electrical conductivity for improving positive electrode is very necessary
's.
The content of the invention
In view of this, it is a primary object of the present invention to provide a kind of nickel cobalt manganese lithium ion cell positive material of vanadium doping
Material, solves the problems, such as that existing positive electrode electrical conductivity is low, specific discharge capacity is low；The present invention also aims to provide the positive pole
The preparation method of material, it this method solve doped chemical skewness in the prior art, guiding discharge specific capacity and conductance
The problem of rate is unbalance.
To reach above-mentioned purpose, the technical proposal of the invention is realized in this way：A kind of nickel cobalt manganese lithium ion of vanadium doping
Cell positive material, its chemical expression are：LiaNixCoyMnzVbO2, wherein 1≤a≤1.2；0.3≤x≤0.98；0.01≤y
≤0.6；0.001≤z≤0.6；B=4/5-a/5-3x/5-3y/5-3z/5,0.00001≤b≤0.2.
What another technical scheme of the present invention was realized in：A kind of nickel cobalt manganese lithium ion cell positive material of vanadium doping
The preparation method of material, this method are achieved by the steps of：
Step 1, polycrystalline nickel cobalt manganese composite precursor, monocrystalline nickel cobalt manganese composite precursor, nanoscale five is weighed respectively to aoxidize
Two vanadium and lithium source；
Step 2, the compound of the monocrystalline nickel cobalt manganese composite precursor described in step 1 and nanoscale vanadium is added into ultrahigh speed
Mixed in blender, obtain the first mixture；
Step 3, the first mixture step 2 obtained and the polycrystalline nickel cobalt manganese composite precursor described in step 1
And lithium source is added in high speed blender and mixed, and obtains the nickel cobalt manganese presoma of vanadium doping；
Step 4, the nickel cobalt manganese presoma of the vanadium doping step 3 obtained, which is fitted into porcelain boat, to be calcined, and obtains vanadium
The nickel cobalt manganese anode material for lithium-ion batteries of doping.
Preferably, in the step 1, the polycrystalline nickel cobalt manganese composite precursor and the monocrystalline nickel cobalt manganese composite precursor
Mass ratio be (2-20)：1.
Preferably, in the step 1, in polycrystalline nickel cobalt manganese composite precursor and monocrystalline the nickel cobalt manganese composite precursor
Nickel, cobalt, manganese mole the ratio between be (0.3-0.98)：(0.01-0.6)：(0.001-0.1).
Preferably, in the step 1, the amount of weighing of the nanoscale vanadic anhydride is nickel, cobalt, manganese integral molar quantity
0.0001-2%.
Preferably, in the step 1, the amount of weighing of lithium source lithium in molar ratio：Me=(1.2-0.9):1 calculates, its
In, Me is nickel, cobalt, the mole sum of manganese.
Preferably, in the step 1, the polycrystalline nickel cobalt manganese composite precursor and the monocrystalline nickel cobalt manganese composite precursor
It is the one or more in nickel, cobalt, the complex hydroxide of manganese, composite oxides, compound oxyhydroxide.
Preferably, in the step 1, the lithium source be lithium nitrate, lithium acetate, lithium carbonate and lithium hydroxide in one kind or
It is a variety of.
Preferably, in the step 2, the rotating speed of the ultrahigh speed blender is 5500-20000r/min.
Preferably, in the step 3, the rotating speed of the high speed blender is 500-10000r/min.
Preferably, in the step 4, the sintering temperature is 600-1200 DEG C, roasting time 6-36h.
Positive electrode of the present invention effectively provides its electrical conductivity and electric discharge specific volume by mixing the compound of nanoscale vanadium
Amount；The inventive method first passes through carries out ultrahigh speed premixing by the compound of monocrystalline nickel cobalt manganese composite precursor and vanadium, then will be single
The compound of brilliant nickel cobalt manganese presoma and vfanadium compound and common polycrystalline nickel cobalt manganese presoma mixed at high speed, improve v element
Effect is uniformly distributed, because monocrystalline composite precursor high mechanical strength, can use ultra-high-speed mixing, and is unlikely to broken, together
Shi Danjing composite precursors can play a part of collision medium, and the compound of vanadium is fully broken up, and make doped chemical and pivot
Element is sufficiently mixed.
Embodiment
In order to make the purpose , technical scheme and advantage of the present invention be clearer, with reference to embodiments, to the present invention
It is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, it is not used to
Limit the present invention.
The embodiments of the invention provide a kind of nickel cobalt manganese anode material for lithium-ion batteries of vanadium doping, its chemical expression
For：LiaNixCoyMnzVbO2, wherein 1≤a≤1.2；0.3≤x≤0.98；0.01≤y≤0.6；0.001≤z≤0.6；B=4/
5-a/5-3x/5-3y/5-3z/5,0.00001≤b≤0.2.
The embodiment of the present invention additionally provides the preparation method of the anode material for lithium-ion batteries, and this method is as follows
Realize：
Step 1, it is (2-20) according to mass ratio：1 to weigh nickel cobalt manganese mol ratio respectively be (0.3-0.98)：(0.01-
0.6)：The polycrystalline nickel cobalt manganese composite precursor and monocrystalline nickel cobalt manganese composite precursor of (0.001-0.1) and a certain amount of nanometer
Vanadic anhydride (V2O5) and lithium source；Wherein, polycrystalline nickel cobalt manganese composite precursor and the monocrystalline nickel cobalt manganese composite precursor are
One or more in nickel, cobalt, the complex hydroxide of manganese, composite oxides, compound oxyhydroxide；The oxidation of nanoscale five two
The amount of weighing of vanadium is nickel, cobalt, the 0.0001-2% of manganese integral molar quantity；The amount of weighing of lithium source lithium in molar ratio：Me=(1.2-
0.9):1 calculates, and Me is nickel, cobalt, the mole sum of manganese；Lithium source is in lithium nitrate, lithium acetate, lithium carbonate and lithium hydroxide
It is one or more；
Step 2, it is by the compound of the monocrystalline nickel cobalt manganese composite precursor described in step 1 and nanoscale vanadium addition rotating speed
Mixed in 5500-20000r/min ultrahigh speed blender, obtain the first mixture；
Step 3, the first mixture step 2 obtained and the polycrystalline nickel cobalt manganese composite precursor described in step 1
And lithium source is added in the high speed blender that rotating speed is 500-10000r/min and mixed, and obtains the nickel cobalt manganese forerunner of vanadium doping
Body；
Step 4, the nickel cobalt manganese presoma of the vanadium doping step 3 obtained is fitted into porcelain boat, at 600-1200 DEG C
6-36h is calcined, obtains the nickel cobalt manganese anode material for lithium-ion batteries of vanadium doping.
Positive electrode of the present invention effectively provides its electrical conductivity and electric discharge specific volume by mixing the compound of nanoscale vanadium
Amount；The inventive method first passes through carries out ultrahigh speed premixing by the compound of monocrystalline nickel cobalt manganese composite precursor and vanadium, then will be single
The compound of brilliant nickel cobalt manganese presoma and vfanadium compound and common polycrystalline nickel cobalt manganese presoma mixed at high speed, improve v element
Effect is uniformly distributed, because monocrystalline composite precursor high mechanical strength, can use ultra-high-speed mixing, and is unlikely to broken, together
Shi Danjing composite precursors can play a part of collision medium, and the compound of vanadium is fully broken up, and make doped chemical and pivot
Element is sufficiently mixed.
Embodiment 1
Prepare LiNi0.98Co0.01Mn1/150V0.002O2Positive electrode；
Step 1, it is 10 according to mass ratio：1 weigh respectively nickel, cobalt, manganese mol ratio be 0.98:0.01:0.006 polycrystalline nickel
Cobalt manganese composite precursor, monocrystalline nickel cobalt manganese composite precursor and a certain amount of nanoscale vanadic anhydride (V2O5) and lithium nitrate
(LiNO3)；Wherein, lithium nitrate (LiNO3) with nickel, cobalt, manganese mole sum ratio be 1:0.997；Nanoscale vanadic anhydride
The amount of weighing for nickel, cobalt, the 0.002% of manganese mole sum；
Step 2, by the monocrystalline nickel cobalt manganese composite precursor and nanoscale V in step 12O5Addition rotating speed is 10000r/min
Ultrahigh speed blender in mixed, obtain the first mixture；
Step 3, the first mixture step 2 obtained and the polycrystalline nickel cobalt manganese composite precursor and nitric acid in step 1
Lithium (LiNO3) rotating speed is added to be mixed in 3000r/min high speed blender, obtain the nickel cobalt manganese presoma of vanadium doping；
Step 4, the nickel cobalt manganese presoma of vanadium doping step 3 obtained is fitted into porcelain boat, is calcined 20h at 900 DEG C, obtains
Obtain the nickel cobalt manganese anode material for lithium-ion batteries (LiNi of vanadium doping0.98Co0.01Mn1/150V0.002O2
), it is designated as positive electrode -1.
Embodiment 2
Prepare LiNi0.98Co0.01Mn1/150V0.002O2Positive electrode；
Step 1, it is 2 according to mass ratio：1 weigh respectively nickel, cobalt, manganese mol ratio be 0.98:0.01:0.006 polycrystalline nickel
Cobalt manganese composite precursor, monocrystalline nickel cobalt manganese composite precursor and a certain amount of nanoscale vanadic anhydride (V2O5) and lithium carbonate
(Li2CO3)；Wherein, lithium carbonate (Li2CO3) with nickel, cobalt, manganese mole sum ratio be 1:0.92；The oxidation of nanoscale five two
The amount of weighing of vanadium is nickel, cobalt, the 0.002% of manganese mole sum；
Step 2, by the monocrystalline nickel cobalt manganese composite precursor and nanoscale V in step 12O5Addition rotating speed is 20000r/min
Ultrahigh speed blender in mixed, obtain the first mixture；
Step 3, the first mixture step 2 obtained and the polycrystalline nickel cobalt manganese composite precursor and carbonic acid in step 1
Lithium (Li2CO3) rotating speed is added to be mixed in 500r/min high speed blender, obtain the nickel cobalt manganese presoma of vanadium doping；
Step 4, the nickel cobalt manganese presoma of vanadium doping step 3 obtained is fitted into porcelain boat, is calcined 36h at 600 DEG C, obtains
Obtain the nickel cobalt manganese anode material for lithium-ion batteries (LiNi of vanadium doping0.98Co0.01Mn1/150V0.002O2), it is designated as positive electrode -2.
Embodiment 3
Prepare LiNi0.98Co0.01Mn1/150V0.002O2Positive electrode；
Step 1, it is 20 according to mass ratio：1 weigh respectively nickel, cobalt, manganese mol ratio be 0.98:0.01:0.006 polycrystalline nickel
Cobalt manganese composite precursor, monocrystalline nickel cobalt manganese composite precursor and a certain amount of nanoscale vanadic anhydride (V2O5) and hydroxide
Lithium (LiOH)；Wherein, lithium hydroxide (LiOH) and the ratio of nickel, cobalt, manganese mole sum are 1:0.997；Nanoscale five aoxidizes
The amount of weighing of two vanadium is nickel, cobalt, the 0.002% of manganese mole sum；
Step 2, by the monocrystalline nickel cobalt manganese composite precursor and nanoscale V in step 12O5Addition rotating speed is 15000r/min
Ultrahigh speed blender in mixed, obtain the first mixture；
Step 3, the first mixture step 2 obtained and the polycrystalline nickel cobalt manganese composite precursor and hydrogen-oxygen in step 1
Change lithium (LiOH) and add rotating speed to be mixed in 5000r/min high speed blender, obtain the nickel cobalt manganese presoma of vanadium doping；
Step 4, the nickel cobalt manganese presoma of vanadium doping step 3 obtained is fitted into porcelain boat, is calcined 6h at 1200 DEG C, obtains
Obtain the nickel cobalt manganese anode material for lithium-ion batteries (LiNi of vanadium doping0.98Co0.01Mn1/150V0.002O2), it is designated as positive electrode -3.
Embodiment 4
Prepare LiNi0.9Co1/75Mn1/300V0.05O2Positive electrode；
Step 1, it is 10 according to mass ratio：1 weigh respectively nickel, cobalt, manganese mol ratio be 0.9:0.013:0.003 polycrystalline nickel
Cobalt manganese composite precursor, monocrystalline nickel cobalt manganese composite precursor and a certain amount of nanoscale vanadic anhydride (V2O5) and lithium nitrate
(LiNO3)；Wherein, lithium nitrate (LiNO3) with nickel, cobalt, manganese mole sum ratio be 1:0.997；Nanoscale vanadic anhydride
The amount of weighing for nickel, cobalt, the 0.05% of manganese mole sum；
Step 2, by the monocrystalline nickel cobalt manganese composite precursor and nanoscale V in step 12O5Addition rotating speed is 10000r/min
Ultrahigh speed blender in mixed, obtain the first mixture；
Step 3, the first mixture step 2 obtained and the polycrystalline nickel cobalt manganese composite precursor and nitric acid in step 1
Lithium (LiNO3) rotating speed is added to be mixed in 3000r/min high speed blender, obtain the nickel cobalt manganese presoma of vanadium doping；
Step 4, the nickel cobalt manganese presoma of vanadium doping step 3 obtained is fitted into porcelain boat, is calcined 20h at 900 DEG C, obtains
Obtain the nickel cobalt manganese anode material for lithium-ion batteries (LiNi of vanadium doping0.9Co1/75Mn1/300V0.05O2), it is designated as positive electrode -4.
Embodiment 5
Prepare LiNi0.9Co1/75Mn1/300V0.05O2Positive electrode；
Step 1, it is 2 according to mass ratio：1 weigh respectively nickel, cobalt, manganese mol ratio be 0.9:0.013:0.003 polycrystalline nickel
Cobalt manganese composite precursor, monocrystalline nickel cobalt manganese composite precursor and a certain amount of nanoscale vanadic anhydride (V2O5) and lithium carbonate
(Li2CO3)；Wherein, lithium carbonate (Li2CO3) with nickel, cobalt, manganese mole sum ratio be 1:0.997；The oxidation of nanoscale five two
The amount of weighing of vanadium is nickel, cobalt, the 0.05% of manganese mole sum；
Step 2, by the monocrystalline nickel cobalt manganese composite precursor and nanoscale V in step 12O5Addition rotating speed is 20000r/min
Ultrahigh speed blender in mixed, obtain the first mixture；
Step 3, the first mixture step 2 obtained and the polycrystalline nickel cobalt manganese composite precursor and carbonic acid in step 1
Lithium (Li2CO3) rotating speed is added to be mixed in 500r/min high speed blender, obtain the nickel cobalt manganese presoma of vanadium doping；
Step 4, the nickel cobalt manganese presoma of vanadium doping step 3 obtained is fitted into porcelain boat, is calcined 36h at 600 DEG C, obtains
Obtain the nickel cobalt manganese anode material for lithium-ion batteries (LiNi of vanadium doping0.9Co1/75Mn1/300V0.05O2), it is designated as positive electrode -5.
Embodiment 6
Prepare LiNi0.9Co1/75Mn1/300V0.05O2Positive electrode；
Step 1, it is 20 according to mass ratio：1 weigh respectively nickel, cobalt, manganese mol ratio be 0.9:0.013:0.003 polycrystalline nickel
Cobalt manganese composite precursor, monocrystalline nickel cobalt manganese composite precursor and a certain amount of nanoscale vanadic anhydride (V2O5) and hydroxide
Lithium (LiOH)；Wherein, lithium hydroxide (LiOH) and the ratio of nickel, cobalt, manganese mole sum are 1:0.997；Nanoscale five aoxidizes
The amount of weighing of two vanadium is nickel, cobalt, the 0.05% of manganese mole sum；
Step 2, by the monocrystalline nickel cobalt manganese composite precursor and nanoscale V in step 12O5Addition rotating speed is 10000r/min
Ultrahigh speed blender in mixed, obtain the first mixture；
Step 3, the first mixture step 2 obtained and the polycrystalline nickel cobalt manganese composite precursor and hydrogen-oxygen in step 1
Change lithium (LiOH) and add rotating speed to be mixed in 3000r/min high speed blender, obtain the nickel cobalt manganese presoma of vanadium doping；
Step 4, the nickel cobalt manganese presoma of vanadium doping step 3 obtained is fitted into porcelain boat, is calcined 6h at 1200 DEG C, obtains
Obtain the nickel cobalt manganese anode material for lithium-ion batteries (LiNi of vanadium doping0.9Co1/75Mn1/300V0.05O2), it is designated as positive electrode -6.
Embodiment 7
Prepare LiNi0.96Co1/75Mn0.01V0.01O2Positive electrode；
Step 1, it is 10 according to mass ratio：1 weigh respectively nickel, cobalt, manganese mol ratio be 0.96:0.013:0.01 polycrystalline nickel
Cobalt manganese composite precursor, monocrystalline nickel cobalt manganese composite precursor and a certain amount of nanoscale vanadic anhydride (V2O5) and lithium nitrate
(LiNO3)；Wherein, lithium nitrate (LiNO3) with nickel, cobalt, manganese mole sum ratio be 1:0.98；Nanoscale vanadic anhydride
The amount of weighing for nickel, cobalt, the 0.01% of manganese mole sum；
Step 2, by the monocrystalline nickel cobalt manganese composite precursor and nanoscale V in step 12O5Addition rotating speed is 10000r/min
Ultrahigh speed blender in mixed, obtain the first mixture；
Step 3, the first mixture step 2 obtained and the polycrystalline nickel cobalt manganese composite precursor and nitric acid in step 1
Lithium (LiNO3) rotating speed is added to be mixed in 3000r/min high speed blender, obtain the nickel cobalt manganese presoma of vanadium doping；
Step 4, the nickel cobalt manganese presoma of vanadium doping step 3 obtained is fitted into porcelain boat, is calcined 20h at 900 DEG C, obtains
Obtain the nickel cobalt manganese anode material for lithium-ion batteries (LiNi of vanadium doping0.96Co1/75Mn0.01V0.01O2), it is designated as positive electrode -7.
Embodiment 8
Prepare LiNi0.96Co1/75Mn0.01V0.01O2Positive electrode；
Step 1, it is 2 according to mass ratio：1 weigh respectively nickel, cobalt, manganese mol ratio be 0.96:0.013:0.01 polycrystalline nickel
Cobalt manganese composite precursor, monocrystalline nickel cobalt manganese composite precursor and a certain amount of nanoscale vanadic anhydride (V2O5) and lithium carbonate
(Li2CO3)；Wherein, lithium carbonate (Li2CO3) with nickel, cobalt, manganese mole sum ratio be 1:0.98；The oxidation of nanoscale five two
The amount of weighing of vanadium is nickel, cobalt, the 0.01% of manganese mole sum；
Step 2, by the monocrystalline nickel cobalt manganese composite precursor and nanoscale V in step 12O5Addition rotating speed is 20000r/min
Ultrahigh speed blender in mixed, obtain the first mixture；
Step 3, the first mixture step 2 obtained and the polycrystalline nickel cobalt manganese composite precursor and carbonic acid in step 1
Lithium (Li2CO3) rotating speed is added to be mixed in 500r/min high speed blender, obtain the nickel cobalt manganese presoma of vanadium doping；
Step 4, the nickel cobalt manganese presoma of vanadium doping step 3 obtained is fitted into porcelain boat, is calcined 36h at 600 DEG C, obtains
Obtain the nickel cobalt manganese anode material for lithium-ion batteries (LiNi of vanadium doping0.96Co1/75Mn0.01V0.01O2), it is designated as positive electrode -8.
Embodiment 9
Prepare LiNi0.96Co1/75Mn0.01V0.01O2Positive electrode；
Step 1, it is 20 according to mass ratio：1 weigh respectively nickel, cobalt, manganese mol ratio be 0.96:0.013:0.01 polycrystalline nickel
Cobalt manganese composite precursor, monocrystalline nickel cobalt manganese composite precursor and a certain amount of nanoscale vanadic anhydride (V2O5) and hydroxide
Lithium (LiOH)；Wherein, lithium hydroxide (LiOH) and the ratio of nickel, cobalt, manganese mole sum are 1:0.98；The oxidation of nanoscale five two
The amount of weighing of vanadium is nickel, cobalt, the 0.01% of manganese mole sum；
Step 2, by the monocrystalline nickel cobalt manganese composite precursor and nanoscale V in step 12O5Addition rotating speed is 10000r/min
Ultrahigh speed blender in mixed, obtain the first mixture；
Step 3, the first mixture step 2 obtained and the polycrystalline nickel cobalt manganese composite precursor and hydrogen-oxygen in step 1
Change lithium (LiOH) and add rotating speed to be mixed in 3000r/min high speed blender, obtain the nickel cobalt manganese presoma of vanadium doping；
Step 4, the nickel cobalt manganese presoma of vanadium doping step 3 obtained is fitted into porcelain boat, is calcined 6h at 1200 DEG C, obtains
Obtain the nickel cobalt manganese anode material for lithium-ion batteries (LiNi of vanadium doping0.96Co1/75Mn0.01V0.01O2), it is designated as positive electrode -9.
Assemble button cell and detection：
Nickel cobalt manganese anode material for lithium-ion batteries using the embodiment 1-9 vanadium dopings obtained is as positive pole, metal lithium sheet
Negative pole, 9 button cells are assembled into respectively and carry out discharge and recharge contrast test, testing result such as following table：
Table 1 is the specific discharge capacity detection of the cell positive material that embodiment 1-9 is obtained and conventional batteries positive electrode
Data
| Specific discharge capacity (mAh/g) under 3C multiplying powers | |
| Positive electrode -1 | 183 |
| Positive electrode -2 | 182 |
| Positive electrode -3 | 184 |
| Positive electrode -4 | 187 |
| Positive electrode -5 | 185 |
| Positive electrode -6 | 183 |
| Positive electrode -7 | 186 |
| Positive electrode -8 | 184 |
| Positive electrode -9 | 183 |
| Conventional material | 177 |
As can be drawn from Table 1：Using the nickel cobalt manganese lithium ion cell positive of 1-9 of the embodiment of the present invention vanadium dopings obtained
The specific discharge capacity of battery made from material is better than the specific discharge capacity of the battery of conventional batteries positive electrode acquisition.
The foregoing is only a preferred embodiment of the present invention, is not intended to limit the scope of the present invention.
Claims (10)
1. the nickel cobalt manganese anode material for lithium-ion batteries of a kind of vanadium doping, it is characterised in that its chemical expression is：
LiaNixCoyMnzVbO2, wherein 1≤a≤1.2；0.3≤x≤0.98；0.01≤y≤0.6；0.001≤z≤0.6；B=4/5-
A/5-3x/5-3y/5-3z/5,0.00001≤b≤0.2.
2. the preparation method of the nickel cobalt manganese anode material for lithium-ion batteries of a kind of vanadium doping, it is characterised in that this method passes through such as
Lower step is realized：
Step 1, polycrystalline nickel cobalt manganese composite precursor, monocrystalline nickel cobalt manganese composite precursor, nanoscale vanadic anhydride are weighed respectively
And lithium source；
Step 2, the compound of the monocrystalline nickel cobalt manganese composite precursor described in step 1 and nanoscale vanadium is added into ultrahigh speed batch mixing
Mixed in device, obtain the first mixture；
Step 3, the first mixture for the step 2 being obtained and the polycrystalline nickel cobalt manganese composite precursor described in step 1 and
Lithium source is added in high speed blender and mixed, and obtains the nickel cobalt manganese presoma of vanadium doping；
Step 4, the nickel cobalt manganese presoma of the vanadium doping step 3 obtained, which is fitted into porcelain boat, to be calcined, and obtains vanadium doping
Nickel cobalt manganese anode material for lithium-ion batteries.
3. a kind of preparation method of the nickel cobalt manganese anode material for lithium-ion batteries of vanadium doping according to claim 2, it is special
Sign is, in the step 1, the mass ratio of the polycrystalline nickel cobalt manganese composite precursor and the monocrystalline nickel cobalt manganese composite precursor
For (2-20)：1.
4. a kind of preparation method of the nickel cobalt manganese anode material for lithium-ion batteries of vanadium doping according to claim 3, it is special
Sign is, in the step 1, nickel in polycrystalline nickel cobalt manganese composite precursor and monocrystalline the nickel cobalt manganese composite precursor, cobalt, manganese
Mole the ratio between be (0.3-0.98)：(0.01-0.6)：(0.001-0.1).
5. a kind of preparation method of the nickel cobalt manganese anode material for lithium-ion batteries of vanadium doping according to claim 4, it is special
Sign is, in the step 1, the amount of weighing of the nanoscale vanadic anhydride is nickel, cobalt, the 0.0001- of manganese integral molar quantity
2%.
6. a kind of preparation method of the nickel cobalt manganese anode material for lithium-ion batteries of vanadium doping according to claim 5, it is special
Sign is, in the step 1, the amount of weighing of lithium source lithium in molar ratio：Me=(1.2-0.9):1 calculates, wherein, Me is
Nickel, cobalt, the mole sum of manganese.
7. a kind of preparation method of the nickel cobalt manganese anode material for lithium-ion batteries of vanadium doping according to claim 6, it is special
Sign is, in the step 1, the polycrystalline nickel cobalt manganese composite precursor and the monocrystalline nickel cobalt manganese composite precursor be nickel,
One or more in cobalt, the complex hydroxide of manganese, composite oxides, compound oxyhydroxide.
8. a kind of preparation method of the nickel cobalt manganese anode material for lithium-ion batteries of vanadium doping according to claim 7, it is special
Sign is, in the step 2, the rotating speed of the ultrahigh speed blender is 5500-20000r/min.
9. a kind of preparation method of the nickel cobalt manganese anode material for lithium-ion batteries of vanadium doping according to claim 8, it is special
Sign is, in the step 3, the rotating speed of the high speed blender is 500-10000r/min.
A kind of 10. system of the nickel cobalt manganese anode material for lithium-ion batteries of vanadium doping according to claim 2-9 any one
Preparation Method, it is characterised in that in the step 4, the sintering temperature is 600-1200 DEG C, roasting time 6-36h.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109616641A (en) * | 2018-12-05 | 2019-04-12 | 成都理工大学 | Li-Ni-Co-Mn-V-O quaternary lithium-ion battery positive electrode material and preparation method thereof |
| CN111313014A (en) * | 2019-10-30 | 2020-06-19 | 河南海宏科技有限公司 | Preparation method of lithium battery positive electrode material with high specific discharge capacity |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102751485A (en) * | 2012-07-17 | 2012-10-24 | 中国电子科技集团公司第十八研究所 | Preparation method of composite cathode material for lithium ion battery |
| CN103840151A (en) * | 2013-12-13 | 2014-06-04 | 山东海特电子新材料有限公司 | Ternary positive electrode material with special single-crystal structure, and preparation method thereof |
| CN105375010A (en) * | 2015-11-26 | 2016-03-02 | 长沙矿冶研究院有限责任公司 | Preparation method of high compaction density lithium ion cathode material |
| CN106602055A (en) * | 2016-11-23 | 2017-04-26 | 广东邦普循环科技有限公司 | Small-granule monocrystal lithium nickel cobalt manganate positive electrode material and preparation method therefor |
-
2017
- 2017-09-27 CN CN201710892818.2A patent/CN107799739A/en not_active Withdrawn
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102751485A (en) * | 2012-07-17 | 2012-10-24 | 中国电子科技集团公司第十八研究所 | Preparation method of composite cathode material for lithium ion battery |
| CN103840151A (en) * | 2013-12-13 | 2014-06-04 | 山东海特电子新材料有限公司 | Ternary positive electrode material with special single-crystal structure, and preparation method thereof |
| CN105375010A (en) * | 2015-11-26 | 2016-03-02 | 长沙矿冶研究院有限责任公司 | Preparation method of high compaction density lithium ion cathode material |
| CN106602055A (en) * | 2016-11-23 | 2017-04-26 | 广东邦普循环科技有限公司 | Small-granule monocrystal lithium nickel cobalt manganate positive electrode material and preparation method therefor |
Non-Patent Citations (1)
| Title |
|---|
| HUALI ZHU等: ""The impact of vanadium substitution on the structure and electrochemical performance of LiNi0.5Co0.2Mn0.3O2"", 《ELECTROCHIMICA ACTA》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109616641A (en) * | 2018-12-05 | 2019-04-12 | 成都理工大学 | Li-Ni-Co-Mn-V-O quaternary lithium-ion battery positive electrode material and preparation method thereof |
| CN111313014A (en) * | 2019-10-30 | 2020-06-19 | 河南海宏科技有限公司 | Preparation method of lithium battery positive electrode material with high specific discharge capacity |
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