CN107706390B - Preparation method of fast ion conductor and conductive polymer dual-modified lithium ion battery ternary positive electrode material - Google Patents
Preparation method of fast ion conductor and conductive polymer dual-modified lithium ion battery ternary positive electrode material Download PDFInfo
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- CN107706390B CN107706390B CN201710934133.XA CN201710934133A CN107706390B CN 107706390 B CN107706390 B CN 107706390B CN 201710934133 A CN201710934133 A CN 201710934133A CN 107706390 B CN107706390 B CN 107706390B
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- 239000010416 ion conductor Substances 0.000 title claims abstract description 54
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 49
- 229920001940 conductive polymer Polymers 0.000 title claims abstract description 44
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical class [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 47
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 41
- 238000000227 grinding Methods 0.000 claims abstract description 34
- 239000000463 material Substances 0.000 claims abstract description 34
- 239000010406 cathode material Substances 0.000 claims abstract description 31
- 238000002156 mixing Methods 0.000 claims abstract description 26
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 24
- 239000011248 coating agent Substances 0.000 claims abstract description 20
- 238000000576 coating method Methods 0.000 claims abstract description 20
- 239000010405 anode material Substances 0.000 claims abstract description 19
- 239000011247 coating layer Substances 0.000 claims abstract description 16
- 238000000498 ball milling Methods 0.000 claims abstract description 9
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 34
- 238000000034 method Methods 0.000 claims description 21
- 238000001354 calcination Methods 0.000 claims description 18
- 229920000767 polyaniline Polymers 0.000 claims description 18
- 239000002243 precursor Substances 0.000 claims description 14
- 239000002253 acid Substances 0.000 claims description 11
- -1 polypyridine Polymers 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 10
- 229910015872 LiNi0.8Co0.1Mn0.1O2 Inorganic materials 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- 238000007500 overflow downdraw method Methods 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000003837 high-temperature calcination Methods 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 6
- 239000000178 monomer Substances 0.000 claims description 6
- 238000004321 preservation Methods 0.000 claims description 6
- 230000000630 rising effect Effects 0.000 claims description 4
- 239000007800 oxidant agent Substances 0.000 claims description 3
- 230000001590 oxidative effect Effects 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
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- 229910016104 LiNi1 Inorganic materials 0.000 claims description 2
- 229910001228 Li[Ni1/3Co1/3Mn1/3]O2 (NCM 111) Inorganic materials 0.000 claims description 2
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- 229910052593 corundum Inorganic materials 0.000 claims description 2
- YNQRWVCLAIUHHI-UHFFFAOYSA-L dilithium;oxalate Chemical compound [Li+].[Li+].[O-]C(=O)C([O-])=O YNQRWVCLAIUHHI-UHFFFAOYSA-L 0.000 claims description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 2
- 238000011068 loading method Methods 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 229920006389 polyphenyl polymer Polymers 0.000 claims description 2
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- 229920000123 polythiophene Polymers 0.000 claims description 2
- 238000010189 synthetic method Methods 0.000 claims description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 2
- WQEVDHBJGNOKKO-UHFFFAOYSA-K vanadic acid Chemical compound O[V](O)(O)=O WQEVDHBJGNOKKO-UHFFFAOYSA-K 0.000 claims description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 2
- 230000009977 dual effect Effects 0.000 claims 2
- 230000002194 synthesizing effect Effects 0.000 claims 1
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 abstract description 20
- YQNQTEBHHUSESQ-UHFFFAOYSA-N lithium aluminate Chemical compound [Li+].[O-][Al]=O YQNQTEBHHUSESQ-UHFFFAOYSA-N 0.000 abstract description 3
- 238000010532 solid phase synthesis reaction Methods 0.000 abstract description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 22
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 18
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- 230000000052 comparative effect Effects 0.000 description 12
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- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- 229910052782 aluminium Inorganic materials 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 239000002002 slurry Substances 0.000 description 8
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- 239000000203 mixture Substances 0.000 description 7
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- 239000010410 layer Substances 0.000 description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 5
- 229910017223 Ni0.8Co0.1Mn0.1(OH)2 Inorganic materials 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
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- 230000008569 process Effects 0.000 description 4
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- 229910052720 vanadium Inorganic materials 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
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- 229910052804 chromium Inorganic materials 0.000 description 3
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 3
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- 229920000642 polymer Polymers 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 229910013191 LiMO2 Inorganic materials 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
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- 229910052788 barium Inorganic materials 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
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- 239000008367 deionised water Substances 0.000 description 1
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- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
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- 229910052715 tantalum Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
Images
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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
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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
-
- 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
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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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- 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
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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 invention discloses a preparation method of a fast ion conductor and conductive polymer dual-modified lithium ion battery ternary positive electrode material. The material takes a ternary anode material of a lithium ion battery as a core, a fast ion conductor as a first coating layer, a conductive polymer as a second coating layer, and the fast ion conductor is any one of lithium vanadate, lithium metaaluminate and lithium zirconate. Firstly, uniformly mixing a fast ion conductor and a ternary cathode material, grinding, then coating the fast ion conductor on the ternary cathode material by using a high-temperature solid phase method, then uniformly mixing a conductive polymer and the ternary cathode material coated with the fast ion conductor, carrying out ball milling, coating the conductive polymer on the ternary cathode material coated with the fast ion conductor, and finally obtaining the ternary cathode material of the lithium ion battery, wherein the fast ion conductor and the conductive polymer are doubly modified. The invention combines the fast ion conductor and the conductive polymer to modify the ternary cathode material, so that the ternary cathode material has excellent cycle performance and good rate performance.
Description
Technical Field
The invention belongs to the field of preparation of lithium ion battery materials, and particularly relates to a preparation method of a fast ion conductor and conductive polymer dual-modified lithium ion battery ternary positive electrode material.
Background
Lithium ion batteries have the advantages of high energy density, long cycle life, wide working range and the like, and therefore have great and attractive demands in the fields of portable electronic equipment, electric automobiles, space technology and the like. With the increase of the demand of the market for the endurance mileage of the electric automobile, the lithium ion battery is required to have higher energy density, safety performance and rate capability. However, the energy density of the currently marketed anode material is low, which limits the popularization of the anode material in some fields. Therefore, the improvement of the specific capacity and the rate capability of the ternary cathode material of the lithium ion battery becomes a hot point of current research. Aiming at market demands, the lithium ion battery anode material mainly adopts doping, cladding, optimized synthesis process and the like to improve the performance. The coating technology is one of the methods which are most widely applied and have the best effect at present, namely, the specific capacity, the cycle performance, the rate capability and the like of the anode material are improved by coating a layer of oxide or other salt substances on the surface of the anode material. For example, patent (CN 104466139 a) discloses a method for preparing a conductive polyaniline-coated germanium-doped lithium manganate composite cathode material, wherein the chemical formula of the germanium-doped lithium manganate is LiMn1-x-yAlxGeyO2After the conductive polyaniline is used for coating the germanium-doped lithium manganate composite positive electrode material, an electrical property test is carried out at 25 ℃, and the specific capacity is increased by 32-35% and the service life is prolonged by more than 40%.
The fast ion conductor has wide application prospect in the fields of high-energy high-density batteries, electrochemical energy storage and the like. Taking lithium vanadate as an example, the lithium vanadate has a layered structure and high specific capacity, and can effectively improve the cycle performance of the ternary material. However, vanadium contains a plurality of valence states, and it is difficult to identify a synthesized component, and the coating tends to be nonuniform. Therefore, the modification of the ternary cathode material by using lithium vanadate needs to be further improved. The conductive polymer is a kind of polymer which is transformed into a conductor by chemical or electrochemical doping from a polymer with conjugated pi-pi bonds, and is an ideal electrode material of a secondary battery. Taking polyaniline as an example, the main chain of the ternary positive electrode material contains alternate benzene rings and nitrogen atoms, so that the ternary positive electrode material has the characteristics of easiness in synthesis, easiness in processing, good conductivity and the like, and the rate capability of the ternary positive electrode material can be improved to a certain extent by using the conductive polyaniline.
Therefore, the advantages of the fast ionic conductor and the conductive polymer are integrated, the ternary cathode material is modified, the defect caused by uneven coating of the ternary cathode material is overcome, the cycle performance and the rate capability of the ternary cathode material are improved, and a good solution is provided for meeting the demand of the lithium ion battery in the fast charging direction.
Patent 201210346551.4 discloses a lithium ion battery positive electrode material and a preparation method thereof, which also includes a positive electrode active material, a fast ion conductor layer coated on the surface of the positive electrode active material, and a conductive polymer layer. The difference between this patent and the present invention is that the fast ion conductor composition used is different, and the composition of the fast ion conductor layer is the fast ion conductor Li of garnet structure5+x+yN3-xM2-yO12Wherein, N is one or more of La, Al, Sr, Sc, Cr, Ba, Fe, Mo and Y; m is one or more of Ta, Nb and V; x is more than or equal to 0 and less than or equal to 2, and y is more than or equal to 0 and less than or equal to 1. The invention adopts the fast ion conductor as any one of lithium vanadate, lithium metaaluminate and lithium zirconate, and has the advantages of different components, more universal materials, simple preparation and lower cost. And the preparation method of the invention is completely different from the method. The patent prepares various raw materials and positive active materials which form the fast ion conductor into slurry and then calcines the slurry to obtain a coating layer of the fast ion conductor; the conductive polymer layer is also formed by adding the lithium ion battery anode material coated with the fast ion conductor layer into protonic acid, stirring, adding a conductive polymer monomer, adding an oxidant, reacting, washing and drying. The invention is prepared by grinding or mechanically ball milling or high-speed mixing the finished product of the fast ionic conductor and the conductive polymer and the ternary anode material, and then calcining at high temperature and coating. The method is simpler and more convenient, and has low cost and good effect; the capacity retention rate of the prepared anode material is higher than 90% under 100 cycles, and the discharge specific capacity is up to 160mAh/g under 5C.
Disclosure of Invention
The invention aims to provide a preparation method of a fast ion conductor and conductive polymer dual-modified lithium ion battery ternary positive electrode material. Compared with the prior art, the method is simple to operate, easy to industrialize and cost-saving; meanwhile, the anode material prepared by the method has good cycle performance, rate capability and specific capacity, and provides a choice for a quick charge material of a lithium ion battery.
The purpose of the invention is realized by the following modes:
a preparation method of a fast ion conductor and conductive polymer double-modified lithium ion battery ternary positive electrode material comprises the following steps: the material is a ternary anode material LiMO2Taking the core as a core, wherein M is any three of Ni, Co, Mn, Al, Fe, Zn, V, Mg and Cr, the fast ion conductor is a first coating layer, the conductive polymer is a second coating layer, and the fast ion conductor is any one of lithium vanadate, lithium metaaluminate and lithium zirconate; the preparation method of the fast ion conductor and conductive polymer double-modified lithium ion battery ternary positive electrode material comprises the following steps: firstly, uniformly mixing a fast ion conductor and a ternary cathode material, grinding, then coating the fast ion conductor on the ternary cathode material by a high-temperature solid phase method, then uniformly mixing and mechanically fusing a conductive polymer and the ternary cathode material coated with the fast ion conductor, coating the conductive polymer on the ternary cathode material coated with the fast ion conductor, and finally obtaining the ternary cathode material of the lithium ion battery, wherein the fast ion conductor and the conductive polymer are doubly modified.
As further preferred: the ternary positive electrode material is LiNi0.8Co0.1Mn0.1O2，LiNi0.5Co0.2Mn0.3O2，LiNi1/3Co1/3Mn1/3O2，LiNi1/3Co1/3Fe1/3O2Any one of them.
As further preferred: the conductive polymer is any one of polypyrrole, polyaniline, polypyridine, polyphenyl, polyphenylene ethylene and polythiophene.
As further preferred: the thickness of the fast ion conductor coating layer is 5-3000 nm, preferably 20-100 nm, the thickness of the conductive polymer coating layer is 1-2000nm, preferably 10-50nm, and the particle size of the coated material is 1-50 microns, preferably 20-50 microns; the mass ratio of the fast ion conductor, the conductive polymer and the ternary anode material is (1-20): 1-10): 100.
The preparation method of the fast ion conductor and conductive polymer double-modified lithium ion battery ternary cathode material comprises the following specific steps:
(1) the synthetic method of the ternary cathode material comprises the following steps: fully grinding a lithium source, uniformly stirring and mixing a precursor of the ternary material and the lithium source according to a mass ratio of (1: 1-1: 1.1), and then calcining the uniformly mixed material at high temperature;
(2) uniformly mixing an oxide or an acid with a hydroxide according to a stoichiometric ratio (1: 1-8: 1), grinding until a fast ion conductor is completely generated, adding the ternary cathode material prepared in the step (1) in proportion, uniformly mixing and grinding until a coating is uniformly coated, and calcining at high temperature to obtain the ternary cathode material taking the fast ion conductor as a first coating;
(3) mixing a conductive polymer monomer, an oxidant and corresponding acid in a certain sequence and proportion, stirring at room temperature, washing, and drying to obtain a conductive polymer for later use; and (3) weighing the conductive polymer and the ternary cathode material which is synthesized in the step (2) and takes the fast ion conductor as the first coating layer according to the mass ratio, uniformly mixing, and adopting a mechanical fusion method to react to synthesize the ternary cathode material of the lithium ion battery, which takes the fast ion conductor as the first coating layer and takes the conductive polymer as the second coating layer, namely the fast ion conductor and the conductive polymer are doubly modified.
As further preferred: fully grinding a lithium source into 1-50 microns, and then stirring and uniformly mixing a precursor of the ternary material and the lithium source; the lithium source is: one or more of lithium hydroxide, lithium carbonate and lithium oxalate;
as further preferred: the precursor of the ternary material is as follows: LiM (OH) n, wherein M is any three of Ni, Co, Mn, Al, Fe, Zn, V, Mg and Cr, and 0<n<8; the atmosphere is O during high-temperature calcination2，Ar，N2Heating up any one of air at a speed of 3-10 ℃/min, keeping the temperature at 400-1200 ℃ during calcination, and keeping the temperature for 3-72 h; preferably, the heat preservation temperature is 750-800 ℃ and the heat preservation time is 10-20h during calcination.
As further preferred: the oxide in the step (2) is: v2O5，Al2O3，TiO2The acid is any one or more of metatitanic acid, metaaluminic acid and vanadic acid, and the hydroxide is lithium-containing hydroxide.
As further preferred: the atmosphere is O during high-temperature calcination in the step (2)2，Ar，N2The temperature rising speed of any one of the air is 3-10 ℃/min, the heat preservation temperature during calcination is 400-1200 ℃, and the heat preservation time is 3-72 h. Preferably, the temperature is 700-900 ℃ during calcination, and the time is 5-8 h.
As further preferred: the mechanical fusion method adopted in the step (3) is a ball milling method.
As further preferred: the frequency of the ball mill is 1-50Hz, the time is 5-120min, preferably the frequency of the ball mill is 10-25Hz, the time is 5-20min, the volume of the grinding balls filled in the tank accounts for 10-30% of the volume of the tank, the material filling amount accounts for 5-30% of the volume of the tank, the diameters of the grinding balls are respectively 1cm and 0.6cm, and the number ratio is 1: 4-1: 5.
The invention has the following advantages:
1. the invention integrates the advantages of the fast ion conductor and the conductive polymer, comprehensively modifies the ternary anode material, overcomes the defects caused by uneven coating of the ternary anode material, and the prepared anode material has good cycle performance, rate capability and specific capacity; a good solution is provided for meeting the requirement of the lithium ion battery in the quick charging direction.
2. Compared with the prior art, the method has the advantages of simple operation steps, easily obtained raw materials, low cost, easy industrialization and great cost saving.
3. Compared with the prior art, the method effectively avoids the damage of the raw material structure and the damage of the material performance caused by easy water absorption of part of ternary materials in the preparation process.
4. In the process of preparing the ternary material, the ternary material and a lithium source are mixed and ground and then calcined to obtain a finished product in the prior art, the experimental method comprises the steps of grinding the lithium source to 1-50 microns, uniformly mixing the precursor of the ternary material and the precursor of the ternary material, and finally calcining, compared with the prior art, the process reduces the appearance damage of the ternary material in the ball milling process, effectively improves the utilization rate of the material, and improves the performance of the material.
Drawings
Fig. 1 is an SEM image of the cathode material prepared in examples 1 and 2;
FIG. 2 is a TEM image of the positive electrode material prepared in examples 1 and 2;
FIG. 3 is a graph showing the first charge and discharge curves at 0.1C for the positive electrode materials prepared in examples 1 and 2 and comparative examples 1, 2, 3 and 4;
FIG. 4 is a graph of cycle performance at 1C for positive electrode materials prepared in examples 1 and 2 and comparative examples 1, 2, 3 and 4;
fig. 5 is a graph showing cycle performance of the positive electrode materials prepared in examples 1 and 2 and comparative examples 1, 2, 3 and 4 at different rates.
Detailed Description
The present invention is further described below in conjunction with the preferred embodiments, and it should be noted that, for those skilled in the art, various modifications and improvements can be made without departing from the principle of the embodiments of the present invention, and these modifications and improvements are also considered to be within the scope of the present invention.
In the embodiment, the fast ion conductor adopts lithium vanadate, the conductive polymer adopts conductive polyaniline, and the ternary positive electrode material adopts LiNi0.8Co0.1Mn0.1O2。
Example 1
Mixing Ni0.8Co0.1Mn0.1(OH)2Precursor and LiOH. H2Mixing O according to the molar ratio of 1:1.07, fully grinding, heating at the speed of 5 ℃/min in the oxygen atmosphere, calcining at the high temperature of 750 ℃ for 15h, and finally obtaining the LiNi of the lithium ion battery0.8Co0.1Mn0.1O2And (3) a positive electrode material. V is then weighed in an amount of 3 wt.% of coating2O5Reacting LiOH. H2O and V2O5Mixing and grinding the mixture according to the molar ratio of 3:1 for 10min to react V2O5The reaction is completed to generate lithium vanadate, and LiNi is added0.8Co0.1Mn0.1O2And continuously grinding the positive electrode material for 30min until the generated lithium vanadate has no obvious agglomeration phenomenon, so that the lithium vanadate is fully reacted and uniformly attached to the surface of the positive electrode material, and calcining the fully ground material at 700 ℃ for 8h by adopting a high-temperature calcination method to obtain the lithium ion battery LiNi modified by the fast ion conductor lithium vanadate0.8Co0.1Mn0.1O2And (3) a positive electrode material. Meanwhile, 2mL of distilled aniline monomer and 3g of Ammonium Persulfate (APS) were dissolved in 40mL of 1mol/L hydrochloric acid solution, and then the ammonium persulfate solution was added dropwise to the aniline solution and stirred at room temperature for 4 hours. And (4) centrifugally washing and drying for 8 hours to obtain the conductive polyaniline for later use. Finally, the conductive polyaniline and lithium vanadate modified lithium ion battery LiNi are weighed according to the coating amount of 1 wt%0.8Co0.1Mn0.1O2The positive electrode material is fully ground by a mechanical fusion method by using a ball mill, the frequency of the ball mill is 30Hz, the time is 10min, the volume of grinding balls filled in a tank accounts for 10% of the volume of the tank, the material loading accounts for 5% of the volume of the tank, the diameters of the grinding balls are respectively 1cm and 0.6cm, and the quantity ratio is 1: 4. Obtaining the LiNi of the lithium ion battery doubly modified by the conductive polyaniline and the lithium vanadate0.8Co0.1Mn0.1O2And (3) a positive electrode material.
The final product obtained was as active substance: acetylene black: PVDF (polyvinylidene fluoride) is mixed and ground uniformly in a ratio of 8:1:1, then a proper amount of NMP (N-methyl pyrrolidone) is added to prepare slurry, the slurry is uniformly coated on a 0.02mm aluminum foil, and the aluminum foil is placed in a vacuum drying oven to be dried for 8 hours at 100 ℃ to prepare a positive plate with the diameter of 14 mm.
Example 2
Firstly, LiOH. H2Ball milling for 30min to 1-20 micron, and adding Ni0.8Co0.1Mn0.1(OH)2Precursor and LiOH. H2O is uniformly mixed according to the molar ratio of 1:1.05, and is calcined for 15 hours at the high temperature of 780 ℃ at the heating rate of 5 ℃/min in the oxygen atmosphere to obtain the LiNi of the lithium ion battery0.8Co0.1Mn0.1O2And (3) a positive electrode material. V is then weighed in an amount of 1 wt.% of coating2O5Reacting LiOH. H2O and V2O5Mixing and grinding the mixture according to the molar ratio of 3:1 for 10min to react V2O5Lithium vanadate is generated after the reaction is completed, LiNi is added0.8Co0.1Mn0.1O2And continuously grinding the positive electrode material for 30min to uniformly mix the generated lithium vanadate with the positive electrode material, so that the lithium vanadate is fully reacted and uniformly attached to the surface of the positive electrode material, and calcining the fully ground material at 700 ℃ for 8h by adopting a high-temperature calcination method to obtain lithium vanadate modified lithium ion battery LiNi0.8Co0.1Mn0.1O2And (3) a positive electrode material. Meanwhile, 2mL of distilled aniline monomer and 3g of Ammonium Persulfate (APS) were dissolved in 40mL of 1mol/L hydrochloric acid solution, and then the ammonium persulfate solution was added dropwise to the aniline solution and stirred at room temperature for 7 hours. And then centrifugally washing and drying for 12 hours to obtain the conductive polyaniline for later use. Finally, the conductive polyaniline and lithium vanadate modified lithium ion battery LiNi are weighed according to the coating amount of 1 wt%0.8Co0.1Mn0.1O2And fully grinding the anode material by using a ball mill by adopting a mechanical fusion method, wherein the frequency of the ball mill is 20Hz, the time is 15min, the volume of the grinding balls filled in the tank accounts for 10% of the volume of the tank, the material filling amount accounts for 5% of the volume of the tank, the diameters of the grinding balls are respectively 1cm and 0.6cm, and the quantity ratio is 1: 4. Obtaining lithium vanadate and conductive polyaniline dual-modified lithium ion battery LiNi0.8Co0.1Mn0.1O2And (3) a positive electrode material.
The final product obtained was as active substance: acetylene black: PVDF (polyvinylidene fluoride) is mixed and ground uniformly in a ratio of 8:1:1, then a proper amount of NMP (N-methyl pyrrolidone) is added to prepare slurry, the slurry is uniformly coated on a 0.02mm aluminum foil, and the aluminum foil is placed in a vacuum drying oven to be dried for 8 hours at 100 ℃ to prepare a positive plate with the diameter of 14 mm.
Comparative example
Comparative example 1
Weigh 10gLiNi0.8Co0.1Mn0.1O2，0.3gV2O5，0.21gLiOH·H2O，LiOH·H2O and V2O5The molar ratio of the three components is 3:1, then the three components are put into deionized water, stirred evenly and dried. Roasting the dried material in the following roasting mode: heating to 700 ℃ at a speed of 5 ℃/min, preserving heat for 8h, and cooling to obtain lithium vanadate modified lithium ion battery LiNi0.8Co0.1Mn0.1O2And (3) a positive electrode material. The lithium vanadate modified lithium ion battery LiNi0.8Co0.1Mn0.1O2Adding a positive electrode material into 100mL of 1mol/L hydrochloric acid solution, stirring for 10min, wherein the molar ratio of ammonium persulfate to aniline is 1:1, weighing 0.1g of aniline to dissolve the aniline in the 100mL of 1mol/L hydrochloric acid solution, then adding 0.25g of ammonium persulfate into the solution, stirring for 8h, stopping stirring, filtering, washing and drying to obtain the lithium vanadate and conductive polyaniline double-modified lithium ion battery LiNi prepared under the method0.8Co0.1Mn0.1O2And (3) a positive electrode material.
Comparative example 2
Firstly, LiOH. H2Ball milling for 30min to 1-20 micron, and adding Ni0.8Co0.1Mn0.1(OH)2Precursor and LiOH. H2Mixing O uniformly according to the molar ratio of 1:1.05, heating to 780 ℃ at the speed of 5 ℃/min in the oxygen atmosphere, and calcining at high temperature for 15h to obtain LiNi of the lithium ion battery0.8Co0.1Mn0.1O2And (3) a positive electrode material. V is then weighed in an amount of 1 wt.% of coating2O5Reacting LiOH. H2O and V2O5Mixing and grinding the mixture according to the molar ratio of 3:1 for 10min to react V2O5Lithium vanadate is generated after the reaction is completed, LiNi is added0.8Co0.1Mn0.1O2And continuously grinding the positive electrode material for 30min to uniformly mix the generated lithium vanadate with the positive electrode material, so that the lithium vanadate is fully reacted and uniformly attached to the surface of the positive electrode material, and finally, calcining the fully ground material at 700 ℃ for 8h by using a high-temperature calcination method to obtain lithium vanadate modified lithium ion battery LiNi0.8Co0.1Mn0.1O2And (3) a positive electrode material.
Comparative example 3
Firstly, LiOH. H2Ball milling for 30min to1-20 μm, adding Ni0.8Co0.1Mn0.1(OH)2Precursor and LiOH. H2O is uniformly mixed according to the molar ratio of 1:1.05, and is calcined at 780 ℃ for 15 hours at the temperature rising speed of 5 ℃/min in the oxygen atmosphere to obtain the LiNi of the lithium ion battery0.8Co0.1Mn0.1O2And (3) a positive electrode material. 2mL of distilled aniline monomer and 3g of Ammonium Persulfate (APS) are dissolved in 40mL of 1mol/L hydrochloric acid solution respectively, and then the ammonium persulfate solution is added dropwise into the aniline solution and stirred at room temperature for 7 hours. And then centrifugally washing and drying for 12 hours to obtain the conductive polyaniline for later use. Conductive polyaniline and LiNi were weighed at a coating amount of 3 wt.%0.8Co0.1Mn0.1O2Fully grinding the anode material by a mechanical fusion method by using a ball mill, wherein the frequency of the ball mill is 20Hz, the time is 15min, the volume of the grinding medium filled in the tank accounts for 10% of the volume of the tank, the material filling amount accounts for 5% of the volume of the tank, the diameters of grinding balls are respectively 1cm and 0.6cm, and the ratio of the grinding balls to the grinding medium is 1: 4. Finally obtaining the lithium ion battery LiNi modified by the conductive polyaniline0.8Co0.1Mn0.1O2And (3) a positive electrode material.
Comparative example 4
Firstly, LiOH. H2Ball milling for 30min to 1-20 micron, and adding Ni0.8Co0.1Mn0.1(OH)2Precursor and LiOH. H2Mixing O uniformly according to the molar ratio of 1:1.05, and calcining at 780 ℃ for 15h at the temperature rising speed of 5 ℃/min in the oxygen atmosphere to finally obtain the LiNi of the lithium ion battery0.8Co0.1Mn0.1O2And (3) a positive electrode material. Meanwhile, Ni is processed by the traditional method0.8Co0.1Mn0.1(OH)2Precursor and LiOH. H2Mixing O according to the molar ratio of 1:1.05, grinding uniformly, and obtaining the LiNi of the lithium ion battery under the same conditions0.8Co0.1Mn0.1O2And (3) a positive electrode material. The latter is far inferior to the former in terms of both electrochemical performance and morphology. The former is mainly because the former effectively prevents the active material from being destroyed, so that only the former is adopted as a comparative example of the experimental part here.
The products obtained in the comparative examples were each as active substance: acetylene black: PVDF (polyvinylidene fluoride) is mixed and ground uniformly in a ratio of 8:1:1, then a proper amount of organic solvent NMP is added to prepare slurry, the slurry is uniformly coated on a 0.02mm aluminum foil, and the aluminum foil is placed into a vacuum drying oven to be dried for 8 hours at 100 ℃ to prepare a positive plate with the diameter of 14 mm.
Finally, the positive electrode sheets obtained in the above examples 1 and 2 and comparative examples 1, 2, 3 and 4 were used as a positive electrode, a negative electrode was used as a metal lithium sheet, a separator was a microporous polypropylene film (Celgard 2300), and an electrolyte was a 1mol/L LiPF6/EC + DMC + EMC (volume ratio 1:1:1) mixed solution. And assembling the positive electrode shell, the positive plate, the diaphragm, the lithium plate, the nickel screen and the negative electrode shell into the button cell in an argon-protected glove box. And standing the assembled battery for 12 hours at room temperature, and then testing the electrochemical performance of the battery by adopting a Wuhan blue electric testing system.
The test result shows that: lithium vanadate and conductive polyaniline doubly-modified lithium ion battery LiNi obtained by the method0.8Co0.1Mn0.1O2The first discharge specific capacity of the anode material at 0.1 ℃ is 218.8mAh/g, after 90 cycles at 1 ℃ the capacity retention rate reaches more than 93%, and the electrochemical performance is obviously superior to that of other comparative examples. Meanwhile, LiNi doubly modified by lithium vanadate and conductive polyaniline synthesized by the method of the invention at high magnification0.8Co0.1Mn0.1O2The positive electrode material has the best rate performance.
Claims (3)
1. A preparation method of a fast ion conductor and conductive polymer dual-modified lithium ion battery ternary positive electrode material is characterized by comprising the following steps:
(1) the synthetic method of the ternary cathode material comprises the following steps: fully grinding a lithium source, uniformly stirring and mixing a precursor of the ternary material and the lithium source according to a mass ratio, and then calcining the uniformly mixed material at a high temperature;
(2) uniformly mixing an oxide or an acid with a hydroxide according to a stoichiometric ratio, grinding until a fast ion conductor is completely generated, adding the ternary cathode material prepared in the step (1) according to a proportion, uniformly mixing and grinding until a coating is uniformly coated, and calcining at a high temperature to obtain the ternary cathode material taking the fast ion conductor as a first coating layer;
(3) mixing a conductive polymer monomer, an oxidant and corresponding acid in a certain sequence and proportion, stirring at room temperature, washing, and drying to obtain a conductive polymer for later use; weighing a conductive polymer and the ternary positive electrode material which is synthesized in the step (2) and takes the fast ion conductor as the first coating layer according to the mass ratio, uniformly mixing, adopting a mechanical fusion method to react, and synthesizing the ternary positive electrode material of the lithium ion battery which takes the fast ion conductor as the first coating layer and takes the conductive polymer as the second coating layer, namely the fast ion conductor and the conductive polymer are doubly modified;
the ternary cathode material in the step (1) is LiNi0.8Co0.1Mn0.1O2，LiNi0.5Co0.2Mn0.3O2，LiNi1/3Co1/ 3Mn1/3O2，LiNi1/3Co1/3Fe1/3O2Any one of the above;
the oxide in the step (2) is: v2O5，Al2O3,TiO2Acid is any one or more of metatitanic acid, metaaluminic acid and vanadic acid, and hydroxide is lithium-containing hydroxide;
the atmosphere is O during high-temperature calcination in the step (2)2，Ar，N2Heating up any one of air at a speed of 3-10 ℃/min, keeping the temperature at 400-1200 ℃ during calcination, and keeping the temperature for 3-72 h;
the mechanical fusion method adopted in the step (3) is a ball milling method; the frequency of the ball mill is 1-50Hz, the time is 5-120min, the volume of the grinding balls filled in the tank accounts for 10% -30% of the volume of the tank, the material loading accounts for 5% -30% of the volume of the tank, the diameters of the grinding balls are respectively 1cm and 0.6cm, and the quantity ratio is 1: 4-1: 5;
the thickness of the fast ion conductor coating layer is 5-3000 nm, the thickness of the conductive polymer coating layer is 1-2000nm, the particle size of the coated material is 1-50 microns, and the mass ratio of the fast ion conductor, the conductive polymer and the ternary anode material is (1-20): 1-10): 100.
2. The preparation method of the fast ion conductor and conductive polymer dual modified lithium ion battery ternary cathode material according to claim 1, characterized in that: the conductive polymer is any one of polypyrrole, polyaniline, polypyridine, polyphenyl, polyphenylene ethylene and polythiophene.
3. The preparation method of the fast ion conductor and conductive polymer dual modified lithium ion battery ternary cathode material according to claim 1, characterized in that:
fully grinding a lithium source into 1-50 microns, and then stirring and uniformly mixing a precursor of the ternary material and the lithium source; the lithium source is: one or more of lithium hydroxide, lithium carbonate and lithium oxalate;
the precursor of the ternary material is calcined at high temperature in an atmosphere of O2，Ar，N2The temperature rising speed of any one of the air is 3-10 ℃/min, the heat preservation temperature during calcination is 400-1200 ℃, and the heat preservation time is 3-72 h.
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