CN114171733B - Coated lithium ion battery positive electrode material and preparation method and application thereof - Google Patents
Coated lithium ion battery positive electrode material and preparation method and application thereof Download PDFInfo
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- CN114171733B CN114171733B CN202111442467.8A CN202111442467A CN114171733B CN 114171733 B CN114171733 B CN 114171733B CN 202111442467 A CN202111442467 A CN 202111442467A CN 114171733 B CN114171733 B CN 114171733B
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 117
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 116
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000010936 titanium Substances 0.000 claims abstract description 96
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 claims abstract description 93
- 239000011247 coating layer Substances 0.000 claims abstract description 75
- 239000010405 anode material Substances 0.000 claims abstract description 72
- 229910001947 lithium oxide Inorganic materials 0.000 claims abstract description 55
- 229910010413 TiO 2 Inorganic materials 0.000 claims abstract description 39
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 33
- 239000011248 coating agent Substances 0.000 claims abstract description 28
- 238000000576 coating method Methods 0.000 claims abstract description 28
- 239000011159 matrix material Substances 0.000 claims abstract description 27
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 16
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 13
- 230000008021 deposition Effects 0.000 claims abstract description 11
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000001301 oxygen Substances 0.000 claims abstract description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 32
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 25
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 24
- 239000010406 cathode material Substances 0.000 claims description 16
- 238000000151 deposition Methods 0.000 claims description 16
- 239000004408 titanium dioxide Substances 0.000 claims description 16
- 239000002245 particle Substances 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 229910001868 water Inorganic materials 0.000 claims description 13
- 239000000126 substance Substances 0.000 claims description 12
- 229910052720 vanadium Inorganic materials 0.000 claims description 12
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 238000000231 atomic layer deposition Methods 0.000 claims description 8
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 8
- LZWQNOHZMQIFBX-UHFFFAOYSA-N lithium;2-methylpropan-2-olate Chemical compound [Li+].CC(C)(C)[O-] LZWQNOHZMQIFBX-UHFFFAOYSA-N 0.000 claims description 8
- 229910052748 manganese Inorganic materials 0.000 claims description 8
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 7
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 7
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 7
- 238000001755 magnetron sputter deposition Methods 0.000 claims description 7
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 7
- 229910052786 argon Inorganic materials 0.000 claims description 5
- 239000001307 helium Substances 0.000 claims description 5
- 229910052734 helium Inorganic materials 0.000 claims description 5
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 239000012298 atmosphere Substances 0.000 claims description 4
- 238000005566 electron beam evaporation Methods 0.000 claims description 4
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 claims description 4
- 230000001681 protective effect Effects 0.000 claims description 4
- 239000000463 material Substances 0.000 abstract description 26
- 230000001351 cycling effect Effects 0.000 abstract 1
- 230000002441 reversible effect Effects 0.000 abstract 1
- 229910000572 Lithium Nickel Cobalt Manganese Oxide (NCM) Inorganic materials 0.000 description 20
- HFCVPDYCRZVZDF-UHFFFAOYSA-N [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O Chemical compound [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O HFCVPDYCRZVZDF-UHFFFAOYSA-N 0.000 description 19
- 238000012360 testing method Methods 0.000 description 18
- 125000004122 cyclic group Chemical group 0.000 description 15
- 239000003792 electrolyte Substances 0.000 description 13
- 239000011572 manganese Substances 0.000 description 11
- 239000012300 argon atmosphere Substances 0.000 description 10
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- 239000002033 PVDF binder Substances 0.000 description 8
- 239000004743 Polypropylene Substances 0.000 description 8
- 239000006230 acetylene black Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 230000014759 maintenance of location Effects 0.000 description 8
- 239000012982 microporous membrane Substances 0.000 description 8
- 238000011056 performance test Methods 0.000 description 8
- -1 polypropylene Polymers 0.000 description 8
- 229920001155 polypropylene Polymers 0.000 description 8
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 8
- 229910001290 LiPF6 Inorganic materials 0.000 description 7
- 239000002131 composite material Substances 0.000 description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 238000005137 deposition process Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 229910052759 nickel Inorganic materials 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- PFYQFCKUASLJLL-UHFFFAOYSA-N [Co].[Ni].[Li] Chemical compound [Co].[Ni].[Li] PFYQFCKUASLJLL-UHFFFAOYSA-N 0.000 description 3
- 229910052733 gallium Inorganic materials 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- UQZIWOQVLUASCR-UHFFFAOYSA-N alumane;titanium Chemical compound [AlH3].[Ti] UQZIWOQVLUASCR-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000003487 electrochemical reaction Methods 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 150000002641 lithium Chemical class 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 229910015645 LiMn Inorganic materials 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- SOXUFMZTHZXOGC-UHFFFAOYSA-N [Li].[Mn].[Co].[Ni] Chemical compound [Li].[Mn].[Co].[Ni] SOXUFMZTHZXOGC-UHFFFAOYSA-N 0.000 description 1
- FBDMTTNVIIVBKI-UHFFFAOYSA-N [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] Chemical compound [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] FBDMTTNVIIVBKI-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- JYYOBHFYCIDXHH-UHFFFAOYSA-N carbonic acid;hydrate Chemical compound O.OC(O)=O JYYOBHFYCIDXHH-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000005056 compaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000011262 electrochemically active material Substances 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 206010016766 flatulence Diseases 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- URIIGZKXFBNRAU-UHFFFAOYSA-N lithium;oxonickel Chemical group [Li].[Ni]=O URIIGZKXFBNRAU-UHFFFAOYSA-N 0.000 description 1
- 239000012621 metal-organic framework Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 239000013077 target material Substances 0.000 description 1
- 150000003608 titanium Chemical class 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
-
- 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
- H01M4/52—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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention provides a coated lithium ion battery anode material, a preparation method and application thereof, wherein the coated lithium ion battery anode material comprises a lithium oxide inner core and a coating layer coating the lithium oxide inner core; the coating layer comprises Li 4 Ti 5 O 12 、TiO 2 With Ti 4 O 7 Is a combination of (a) and (b). In the preparation process, lithium oxide is used as a matrix, and a titanium source, an oxygen source and a lithium source are deposited on the matrix by a deposition system to obtain the coated lithium ion battery anode material. The positive electrode material provided by the invention is prepared by coating Li on the inner core 4 Ti 5 O 12 、TiO 2 Ti and 4 O 7 the coating of the high-ion conductivity and high-electron conductivity material is realized, the overall structural stability of the material can be improved, and the reversible specific capacity and the cycling stability of the material are further improved, so that the coating has good application prospect.
Description
Technical Field
The invention belongs to the technical field of battery materials, relates to a lithium ion battery positive electrode material, and in particular relates to a coated lithium ion battery positive electrode material, a preparation method and application thereof.
Background
With the great development of new energy automobiles, the lithium ion battery industry has entered a rapid development stage. The key materials influencing the performance of the lithium ion battery mainly comprise a positive electrode material, a negative electrode material, electrolyte and the like. Among them, the positive electrode material is a major factor currently limiting the battery performance, and its performance also accounts for nearly 40% of the cost of lithium ion batteries.
Currently, the positive electrode material comprises lithium cobaltate, lithium nickel cobalt manganate, lithium nickel cobalt aluminate, lithium manganate or lithium iron phosphate, etc., but the above materials have respective defects. If lithium cobaltate is expensive, the overcharge resistance is poor, and the capacity under low voltage is limited; the nickel cobalt lithium manganate or nickel cobalt lithium aluminate ternary material has the problems of low compaction density, poor compatibility with electrolyte, flatulence and the like; the high-temperature cycle and high-temperature storage performance of lithium manganate are poor; the lithium iron phosphate has the problems of poor low-temperature performance and the like. The coating modification method can improve the surface structure stability of the positive electrode material and improve the cycle performance of the battery under high voltage.
CN 107195899a discloses a method for coating and modifying a lithium ion battery anode material, which comprises the following steps: uniformly mixing the positive electrode material into a solution containing a template agent, an organic solvent, a ligand and an organic titanium salt, transferring the uniformly mixed solution into a high-pressure reaction kettle, and self-assembling the organic metal salt and the ligand into a metal organic framework material under the action of the template agent at high temperature and high pressure, and uniformly coating the surface of the positive electrode material. And carrying out suction filtration, drying and grinding on the obtained product, and calcining to obtain the lithium ion battery anode material coated with the porous titanium dioxide.
CN 108767221a discloses a modified lithium battery positive electrode material, a preparation method and a lithium ion battery, the modified lithium battery positive electrode material provided by the CN 108767221a comprises a positive electrode material and at least a part of coating layer coated on the surface of the positive electrode material, and the coating layer is composed of titanium-aluminum composite oxide. The preparation method comprises the following steps: and mixing the anode material with the titanium-aluminum composite oxide, performing ball milling, and then sintering to obtain the modified anode material for the lithium battery. The gram capacity and the stability of the material are improved through coating.
CN 108615861a discloses a modified lithium ion battery positive electrode material comprising a lithium ion battery positive electrode substrate and a coating layer applied on the positive electrode substrate, the coating layer comprising a high temperature stability material and an electrochemically active material. The lithium ion battery anode material is obtained by sputtering a combination of a high-temperature stable material and an electrochemical active material serving as a target material on a lithium ion battery anode substrate to form a coating layer through a magnetron sputtering technology.
The above technical solution reports coating modification of the cathode material, but there is still room for improvement in the manner of coating and the selection of the coating, and how to obtain a more uniform coating and select a suitable coating is a technical problem to be solved in the art.
Disclosure of Invention
The invention aims to provide a coated lithium ion battery anode material, a preparation method and application thereof, and the lithium oxide inner core is coated with Li 4 Ti 5 O 12 、TiO 2 With Ti 4 O 7 The high ionic conductivity and high electronic conductivity material are coated together, and the coated lithium ion battery anode material with high conductivity, high specific capacity, high multiplying power, quick charge and discharge and long cycle life is obtained.
In order to achieve the aim of the invention, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a coated lithium ion battery cathode material, the coated lithium ion battery cathode material comprising a lithium oxide core and a coating layer coating the lithium oxide core;
the coating layer comprises Li 4 Ti 5 O 12 、TiO 2 With Ti 4 O 7 Is a combination of (a) and (b).
The invention adopts Li 4 Ti 5 O 12 、TiO 2 With Ti 4 O 7 Coating modification of lithium oxide, li 4 Ti 5 O 12 The high ionic conductivity is realized, and the charge transfer between the anode and the electrolyte interface can be improved; li (Li) 4 Ti 5 O 12 With TiO 2 The method has obvious synergistic effect in the electrochemical reaction process, and can improve the electrochemical stability of the material; ti (Ti) 4 O 7 Has the advantages of superhigh conductivity, good electrochemical stability and corrosion resistance, and the like, and can improve the cycle life of the material. The three titanium-containing compounds have good coordination effect, and the composite positive electrode material obtained by the method has better conductivity, specific capacity, multiplying power characteristic, quick charge and discharge property and longer cycle life when being used as a positive electrode material of a lithium ion battery.
In addition, li 4 Ti 5 O 12 、TiO 2 With Ti 4 O 7 The uniform coating layer is formed, so that a physical barrier can be provided, the occurrence of side reactions is suppressed, the chemical attack of the electrolyte is prevented, and the dissolution of the transition metal is reduced.
Preferably, the chemical expression of the lithium oxide includes Li x Ni a Co b Mn c M 1-a-b-c O 2 And/or Li x Fe d M` 1- d PO 4 Wherein M comprises any one or a combination of at least two of Mn, cr, co, ni, V, ti, al, ga, nb or Mg; m' comprises any one or a combination of at least two of Mn, cr, co, ni, V, ti, al, ga, nb or Mg; and a is more than or equal to 0 and less than or equal to 1, b is more than or equal to 0 and less than or equal to 1,0≤c≤1，0 ≤d≤1，0.4≤x≤1.5。
The chemical expression of the lithium oxide is Li x Ni a Co b Mn c M 1-a-b-c O 2 When M comprises any one or a combination of at least two of Mn, cr, co, ni, V, ti, al, ga, nb or Mg, typical but non-limiting combinations include Mn in combination with Cr, co in combination with Ni, V in combination with Ti, al in combination with Ga, nb in combination with Mg, mn in combination with Cr in combination with Ni, co, V, ti in combination with Al, al in combination with Ga, nb in combination with Mg, or Mn, cr, co, ni, V, ti, al, ga, nb in combination with Mg.
The chemical expression of the lithium oxide is Li x Fe d M` 1-d PO 4 When M' comprises any one or a combination of at least two of Mn, cr, co, ni, V, ti, al, ga, nb or Mg, typical but non-limiting combinations include Mn in combination with Cr, co in combination with Ni, V in combination with Ti, al in combination with Ga, nb in combination with Mg, mn in combination with Cr in combination with Ni, co, V, ti in combination with Al, ga, nb in combination with Mg, or Mn, cr, co, ni, V, ti, al, ga, nb in combination with Mg.
In the chemical expression of the lithium oxide according to the present invention, a is 0 to 1, and may be, for example, 0, 0.1, 0.2, 0.4, 0.5, 0.6, 0.8 or 1, but is not limited to the recited values, and other non-recited values within the numerical range are equally applicable.
In the chemical expression of the lithium oxide according to the present invention, b is 0 to 1, and may be, for example, 0, 0.1, 0.2, 0.4, 0.5, 0.6, 0.8 or 1, but is not limited to the recited values, and other non-recited values within the numerical range are equally applicable.
In the chemical expression of the lithium oxide according to the present invention, c is 0 to 1, and may be, for example, 0, 0.1, 0.2, 0.4, 0.5, 0.6, 0.8 or 1, but is not limited to the recited values, and other non-recited values within the numerical range are equally applicable.
In the chemical expression of the lithium oxide according to the present invention, d is 0 to 1, and may be, for example, 0, 0.1, 0.2, 0.4, 0.5, 0.6, 0.8 or 1, but is not limited to the recited values, and other non-recited values within the numerical range are equally applicable.
In the chemical expression of the lithium oxide according to the present invention, x is 0.4 to 1.5, and may be, for example, 0.4, 0.5, 0.6, 0.8, 1, 1.2 or 1.5, but is not limited to the recited values, and other non-recited values within the numerical range are equally applicable.
The lithium oxide core preferably has an average particle diameter of 1 to 20. Mu.m, for example, 1 μm, 3 μm, 5 μm, 8 μm, 10 μm, 12 μm, 15 μm, 16 μm, 18 μm or 20 μm, but not limited to the recited values, and other non-recited values within the range of values are equally applicable.
Preferably, the mass ratio of the coating layer to the lithium oxide core is (0.01-0.2): 1, which may be, for example, 0.01:1, 0.03:1, 0.05:1, 0.06:1, 0.08:1, 0.1:1, 0.12:1, 0.15:1, 0.16:1, 0.18:1 or 0.2:1, but is not limited to the recited values, as are other non-recited values within the range of values.
Preferably, li in the coating layer 4 Ti 5 O 12 、TiO 2 With Ti 4 O 7 The molar ratio of (1) to (0.5-2), for example, may be 1:1:1, 0.5:0.5:1, 0.5:1:1, 0.5:2:1, 1:0.5:0.5, 1:1:0.5, 1:2:0.5, 2:0.5:0.5, 2:0.5:1, 2:2:0.5 or 2:2:1, but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
In a second aspect, the present invention provides a method for preparing the coated lithium ion battery cathode material according to the first aspect, where the preparation method includes the following steps:
and (3) taking the lithium oxide inner core as a matrix, and depositing on the surface of the matrix by utilizing a deposition source to obtain the coated lithium ion battery anode material.
Preferably, the deposition source comprises a titanium source, an oxygen source, and a lithium source.
Preferably, the titanium source comprises any one or a combination of at least two of titanium tetrachloride, tetraisopropyl titanate, tetrabutyl titanate, or titanium dioxide, and typical but non-limiting combinations include titanium tetrachloride and tetraisopropyl titanate, tetraisopropyl titanate and tetrabutyl titanate, tetrabutyl titanate and titanium dioxide, titanium tetrachloride, tetraisopropyl titanate and tetrabutyl titanate, tetraisopropyl titanate, tetrabutyl titanate and titanium dioxide, or titanium tetrachloride, tetraisopropyl titanate, tetrabutyl titanate and titanium dioxide.
Preferably, the oxygen source comprises water.
Preferably, the lithium source comprises any one or a combination of at least two of lithium tert-butoxide, lithium carbonate, lithium hydroxide, lithium acetate, or lithium oxide, typically but not limited to, a combination of lithium tert-butoxide and lithium carbonate, a combination of lithium carbonate and lithium hydroxide, a combination of lithium acetate and lithium oxide, a combination of lithium tert-butoxide, lithium carbonate and lithium hydroxide, a combination of lithium hydroxide, lithium acetate and lithium oxide, or a combination of lithium tert-butoxide, lithium carbonate, lithium hydroxide, lithium acetate and lithium oxide.
Preferably, the method of deposition comprises any one or a combination of at least two of magnetron sputtering, electron beam evaporation, plasma enhanced chemical vapor deposition or atomic layer deposition.
The deposition method provided by the invention is a conventional method in the field, and the specific parameters are not further limited as long as the deposition can be realized, so that the method can be reasonably adjusted according to actual needs by a person skilled in the art.
The invention converts the composition in the deposition layer into Li by depositing a titanium source, an oxygen source and a lithium source 4 Ti 5 O 12 、 TiO 2 With Ti 4 O 7 After that, li 4 Ti 5 O 12 、TiO 2 With Ti 4 O 7 The molar ratio of (2) to (0.5-2) is satisfied.
Preferably, the deposition is performed in a vacuum environment or a protective atmosphere.
Preferably, the gas used in the protective atmosphere comprises any one or a combination of at least two of nitrogen, argon or helium, typically but not limited to combinations of nitrogen and argon, combinations of argon and helium, combinations of nitrogen and helium, or combinations of nitrogen, argon and helium.
In a third aspect, the present invention provides a lithium ion battery, which includes the coated lithium ion battery cathode material of the first aspect.
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, lithium titanate, titanium dioxide and titanium dioxide are simultaneously introduced to modify the composite lithium oxide, and the electronic conductivity and the ionic conductivity of the material are improved by utilizing the coordination effect among the three, so that the specific capacity and the multiplying power performance of the material are improved, and the cycle life of the material is prolonged.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
Example 1
The embodiment provides a coated lithium ion battery anode material, which comprises a lithium oxide inner core and a coating layer coating the lithium oxide inner core; the lithium oxide core is nickel cobalt lithium manganate (NCM 811) with an average particle size of 5 mu m; the coating layer is Li with the mol ratio of 1:1:1 4 Ti 5 O 12 、TiO 2 With Ti 4 O 7 Is a combination of (a); the mass ratio of the coating layer to the lithium oxide core was 0.05:1.
The preparation method of the coated lithium ion battery anode material comprises the following steps:
under the argon atmosphere condition, taking a lithium oxide inner core as a matrix, utilizing tetraisopropyl titanate, water and lithium tert-butoxide to perform atomic layer deposition on the surface of the matrix, and controlling the ratio of Li, ti and O in the deposition process to ensure that Li in the coating layer 4 Ti 5 O 12 、TiO 2 With Ti 4 O 7 The molar ratio of the lithium ion battery anode material to the lithium ion battery anode material is 1:1:1.
Example 2
The embodiment provides a coated lithium ion battery anode material, which is prepared by the following steps ofThe sub-battery anode material comprises a lithium oxide inner core and a coating layer coating the lithium oxide inner core; the lithium oxide core is nickel cobalt lithium manganate (NCM 811) with an average particle size of 3 mu m; the coating layer is Li with the mole ratio of 0.8:0.5:1 4 Ti 5 O 12 、TiO 2 With Ti 4 O 7 Is a combination of (a); the mass ratio of the coating layer to the lithium oxide core was 0.06:1.
The preparation method of the coated lithium ion battery anode material comprises the following steps:
under the condition of nitrogen atmosphere, taking a lithium oxide inner core as a matrix, utilizing titanium tetrachloride, water and lithium acetate to perform atomic layer deposition on the surface of the matrix, and controlling the ratio of Li, ti and O in the deposition process to ensure that Li in the coating layer 4 Ti 5 O 12 、TiO 2 With Ti 4 O 7 The molar ratio of the lithium ion battery anode material to the lithium ion battery anode material is 0.8:0.5:1.
Example 3
The embodiment provides a coated lithium ion battery anode material, which comprises a lithium oxide inner core and a coating layer coating the lithium oxide inner core; the lithium oxide core is nickel cobalt lithium manganate (NCM 811) with an average particle size of 5 mu m; the coating layer is Li with a molar ratio of 1:0.8:1.1 4 Ti 5 O 12 、TiO 2 With Ti 4 O 7 Is a combination of (a); the mass ratio of the coating layer to the lithium oxide core was 0.08:1.
The preparation method of the coated lithium ion battery anode material comprises the following steps:
under the argon atmosphere condition, taking a lithium oxide inner core as a matrix, utilizing tetraisopropyl titanate, water and lithium hydroxide to perform atomic layer deposition on the surface of the matrix, and controlling the ratio of Li, ti and O in the deposition process to ensure that Li in the coating layer 4 Ti 5 O 12 、TiO 2 With Ti 4 O 7 The molar ratio of the lithium ion battery anode material to the lithium ion battery anode material is 1:0.8:1.1.
Example 4
The present embodiment provides a bagThe lithium ion battery comprises a coated lithium ion battery anode material, a lithium ion battery cathode material and a lithium battery cathode material, wherein the coated lithium ion battery anode material comprises a lithium oxide inner core and a coating layer for coating the lithium oxide inner core; the lithium oxide core is nickel cobalt lithium manganate (NCM 811) with an average particle size of 10 mu m; the coating layer is Li with a molar ratio of 2:0.5:1 4 Ti 5 O 12 、TiO 2 With Ti 4 O 7 Is a combination of (a); the mass ratio of the coating layer to the lithium oxide core was 0.1:1.
The preparation method of the coated lithium ion battery anode material comprises the following steps:
under the argon atmosphere condition, taking a lithium oxide inner core as a matrix, utilizing tetraisopropyl titanate, water and lithium acetate to perform electron beam evaporation on the surface of the matrix, and controlling the ratio of Li, ti and O in the electron beam evaporation process to ensure that Li in the coating layer 4 Ti 5 O 12 、TiO 2 With Ti 4 O 7 The molar ratio of the lithium ion battery anode material to the lithium ion battery anode material is 2:0.5:1.
Example 5
The embodiment provides a coated lithium ion battery anode material, which comprises a lithium oxide inner core and a coating layer coating the lithium oxide inner core; the lithium oxide core is nickel cobalt lithium manganate (NCM 811) with an average particle size of 1 μm; the coating layer is Li with the mole ratio of 0.5:0.5:1 4 Ti 5 O 12 、TiO 2 With Ti 4 O 7 Is a combination of (a); the mass ratio of the coating layer to the lithium oxide core was 0.01:1.
The preparation method of the coated lithium ion battery anode material comprises the following steps:
under the argon atmosphere condition, taking a lithium oxide inner core as a matrix, and performing magnetron sputtering on the surface of the matrix by utilizing titanium dioxide, water and lithium oxide, wherein the ratio of Li, ti and O is controlled in the magnetron sputtering process to ensure that Li in the coating layer 4 Ti 5 O 12 、TiO 2 With Ti 4 O 7 The molar ratio of the lithium ion battery anode material to the lithium ion battery anode material is 0.5:0.5:1.
Example 6
The embodiment provides a coated lithium ion battery anode material, which comprises a lithium oxide inner core and a coating layer coating the lithium oxide inner core; the lithium oxide core is nickel cobalt lithium manganate (NCM 811) with an average particle size of 2 mu m; the coating layer is Li with a molar ratio of 2:1:2 4 Ti 5 O 12 、TiO 2 With Ti 4 O 7 Is a combination of (a); the mass ratio of the coating layer to the lithium oxide core was 0.1:1.
The preparation method of the coated lithium ion battery anode material comprises the following steps:
under the argon atmosphere condition, taking a lithium oxide inner core as a matrix, utilizing titanium dioxide, water and lithium oxide to carry out plasma enhanced chemical vapor deposition on the surface of the matrix, and controlling the proportion of Li, ti and O in the plasma enhanced chemical vapor deposition process to ensure that Li in the coating layer 4 Ti 5 O 12 、TiO 2 With Ti 4 O 7 The molar ratio of the lithium ion battery anode material to the lithium ion battery anode material is 2:1:2.
Example 7
The embodiment provides a coated lithium ion battery anode material, which comprises a lithium oxide inner core and a coating layer coating the lithium oxide inner core; the lithium oxide core is nickel cobalt lithium manganate (NCM 811) with an average particle size of 20 mu m; the coating layer is Li with a molar ratio of 1:1:0.5 4 Ti 5 O 12 、TiO 2 With Ti 4 O 7 Is a combination of (a); the mass ratio of the coating layer to the lithium oxide core was 0.2:1.
The preparation method of the coated lithium ion battery anode material comprises the following steps:
under the argon atmosphere condition, taking a lithium oxide inner core as a matrix, utilizing titanium tetrachloride, water and lithium carbonate to perform atomic layer deposition on the surface of the matrix, and controlling the ratio of Li, ti and O in the deposition process to ensure that Li in the coating layer 4 Ti 5 O 12 、TiO 2 With Ti 4 O 7 The molar ratio of (2) is 1:1:0.5, giving the packageAnd (3) a coated lithium ion battery anode material.
Example 8
The embodiment provides a coated lithium ion battery anode material, which comprises a lithium oxide inner core and a coating layer coating the lithium oxide inner core; the lithium oxide core is nickel cobalt lithium manganate (NCM 811) with an average particle size of 10 mu m; the coating layer is Li with the mole ratio of 0.8:0.5:1 4 Ti 5 O 12 、TiO 2 With Ti 4 O 7 Is a combination of (a); the mass ratio of the coating layer to the lithium oxide core was 0.02:1.
The preparation method of the coated lithium ion battery anode material comprises the following steps:
under the argon atmosphere condition, taking a lithium oxide inner core as a matrix, and utilizing tetrabutyl titanate, water and lithium hydroxide to perform magnetron sputtering on the surface of the matrix, wherein the ratio of Li, ti and O is controlled in the magnetron sputtering process to ensure that Li in the coating layer 4 Ti 5 O 12 、TiO 2 With Ti 4 O 7 The molar ratio of the lithium ion battery anode material to the lithium ion battery anode material is 0.8:0.5:1.
Example 9
The present example provides a coated lithium ion battery cathode material, which was the same as example 1 except that the mass ratio of the coating layer to the lithium oxide core was 0.005:1.
Example 10
The present example provided a coated lithium ion battery positive electrode material, the remainder being the same as example 1 except that the mass ratio of the coating layer to the lithium oxide core was 0.3:1.
Example 11
This example provides a coated lithium ion battery positive electrode material, except Li in the coating layer 4 Ti 5 O 12 、 TiO 2 With Ti 4 O 7 The same as in example 1 except that the molar ratio of (2) was 0.2:1:1.
Example 12
The embodiment provides a coated lithium ion battery anode material, except a coating layerLi in (III) 4 Ti 5 O 12 、 TiO 2 With Ti 4 O 7 The same as in example 1 except that the molar ratio of (2) was 1:0.2:1.
Example 13
This example provides a coated lithium ion battery positive electrode material, except Li in the coating layer 4 Ti 5 O 12 、 TiO 2 With Ti 4 O 7 The same as in example 1 except that the molar ratio of (2) was 1:1:0.2.
Example 14
This example provides a coated lithium ion battery positive electrode material, except Li in the coating layer 4 Ti 5 O 12 、 TiO 2 With Ti 4 O 7 The molar ratio of (2) was 4.5:1:1, the remainder being the same as in example 1.
Example 15
This example provides a coated lithium ion battery positive electrode material, except Li in the coating layer 4 Ti 5 O 12 、 TiO 2 With Ti 4 O 7 The molar ratio of (2) was 1:4.5:1, the remainder being the same as in example 1.
Example 16
This example provides a coated lithium ion battery positive electrode material, except Li in the coating layer 4 Ti 5 O 12 、 TiO 2 With Ti 4 O 7 The same as in example 1 except that the molar ratio of (2) was 1:1:4.5.
Example 17
This example provides a coated lithium ion battery positive electrode material, which is the same as example 1 except that nickel cobalt lithium manganate (NCM 811) is replaced with equal mass nickel cobalt lithium aluminate (NCA 622).
Carrying out electrochemical performance test on the obtained coated lithium ion battery anode material, wherein the pole piece ratio is the lithium ion battery anode material, acetylene black and PVDF in a mass ratio of 90:5:5; the metal lithium sheet is a counter electrode, the polypropylene microporous membrane Celgard 2400 is a diaphragm, and 1mol/L LiPF6/EC+DEC+DMC (volume ratio 1:1:1) is used as electrolyte to prepare the CR2025 button cell. Performing constant-current charge and discharge test on the battery by using a LAND battery test system, wherein the initial cyclic discharge specific capacity is 207mAh/g under the current density of 0.1C in a voltage window of 2.5-4.2V, and the capacity retention rate of 500 circles is 80%; at a current density of 1C, the specific capacity of cyclic discharge is 168mAh/g.
Example 18
This example provides a coated lithium ion battery positive electrode material, which is the same as example 1 except that nickel cobalt lithium manganate (NCM 811) is replaced with equal mass nickel cobalt lithium manganate (NCM 622).
Carrying out electrochemical performance test on the obtained coated lithium ion battery anode material, wherein the pole piece ratio is the lithium ion battery anode material, acetylene black and PVDF in a mass ratio of 90:5:5; the metal lithium sheet is a counter electrode, the polypropylene microporous membrane Celgard 2400 is a diaphragm, and 1mol/L LiPF6/EC+DEC+DMC (volume ratio 1:1:1) is used as electrolyte to prepare the CR2025 button cell. Performing constant-current charge and discharge test on the battery by using a LAND battery test system, wherein the initial cyclic discharge specific capacity is 211mAh/g under the current density of 0.1C in a voltage window of 2.5-4.2V, and the capacity retention rate of 500 circles is 86%; at a current density of 1C, the specific capacity of cyclic discharge is 168mAh/g.
Example 19
This example provides a coated lithium ion battery positive electrode material, which is the same as example 1 except that lithium nickel cobalt manganese oxide (NCM 811) is replaced with lithium nickel oxide of equal mass.
Carrying out electrochemical performance test on the obtained coated lithium ion battery anode material, wherein the pole piece ratio is the lithium ion battery anode material, acetylene black and PVDF in a mass ratio of 90:5:5; the metal lithium sheet is a counter electrode, the polypropylene microporous membrane Celgard 2400 is a diaphragm, and 1mol/L LiPF6/EC+DEC+DMC (volume ratio 1:1:1) is used as electrolyte to prepare the CR2025 button cell. Performing constant-current charge and discharge test on the battery by using a LAND battery test system, wherein the initial cyclic discharge specific capacity is 195mAh/g under the current density of 0.1C in a voltage window of 2.5-4.2V, and the capacity retention rate of 500 circles is 87%; at a current density of 1C, the specific capacity of the cyclic discharge is 165mAh/g.
Example 20
This example provides a coated lithium ion battery positive electrode material, which is the same as example 1 except that lithium nickel cobalt manganese (NCM 811) is replaced with equal mass lithium iron phosphate.
Carrying out electrochemical performance test on the obtained coated lithium ion battery anode material, wherein the pole piece ratio is the lithium ion battery anode material, acetylene black and PVDF in a mass ratio of 90:5:5; the metal lithium sheet is a counter electrode, the polypropylene microporous membrane Celgard 2400 is a diaphragm, and 1mol/L LiPF6/EC+DEC+DMC (volume ratio 1:1:1) is used as electrolyte to prepare the CR2025 button cell. Performing constant-current charge and discharge test on the battery by using a LAND battery test system, wherein the initial cyclic discharge specific capacity is 170mAh/g, and the cyclic 500-circle capacity retention rate is 89% under the current density of 0.1C and the voltage window of 2.5-4.2V; at a current density of 1C, the specific capacity of cyclic discharge is 155mAh/g.
Example 21
The present example provides a coated lithium ion battery positive electrode material except that nickel cobalt lithium manganate (NCM 811) is replaced with equal mass Li 1.2 Ni 0.2 Ti 0.6 O 2 Except for this, the procedure was the same as in example 1.
Carrying out electrochemical performance test on the obtained coated lithium ion battery anode material, wherein the pole piece ratio is the lithium ion battery anode material, acetylene black and PVDF in a mass ratio of 90:5:5; the metal lithium sheet is a counter electrode, the polypropylene microporous membrane Celgard 2400 is a diaphragm, and 1mol/L LiPF6/EC+DEC+DMC (volume ratio 1:1:1) is used as electrolyte to prepare the CR2025 button cell. Performing constant-current charge and discharge test on the battery by using a LAND battery test system, wherein the initial cyclic discharge specific capacity is 250mAh/g under the current density of 0.1C in a voltage window of 1.5-4.5V, and the capacity retention rate of 500 circles is 76%; at a current density of 1C, the specific capacity of the cyclic discharge is 192mAh/g.
Example 22
The embodiment provides a coated lithium ion battery positive electrode material except that nickel cobalt lithium manganate (NCM 811) is replaced by LiMn with equal mass 0.75 Fe 0.25 PO 4 Except for this, the procedure was the same as in example 1.
Carrying out electrochemical performance test on the obtained coated lithium ion battery anode material, wherein the pole piece ratio is the lithium ion battery anode material, acetylene black and PVDF in a mass ratio of 90:5:5; the metal lithium sheet is a counter electrode, the polypropylene microporous membrane Celgard 2400 is a diaphragm, and 1mol/L LiPF6/EC+DEC+DMC (volume ratio 1:1:1) is used as electrolyte to prepare the CR2025 button cell. Performing constant-current charge and discharge test on the battery by using a LAND battery test system, wherein the initial cyclic discharge specific capacity is 165mAh/g under the current density of 0.1C in a voltage window of 2.5-4.2V, and the capacity retention rate of 500 circles is 83%; at a current density of 1C, the specific capacity of cyclic discharge is 142mAh/g.
Example 23
The present example provides a coated lithium ion battery positive electrode material except that nickel cobalt lithium manganate (NCM 811) is replaced with equal mass Li 1.2 Mn 0.2 Ti 0.6 O 2 Except for this, the procedure was the same as in example 1.
Carrying out electrochemical performance test on the obtained coated lithium ion battery anode material, wherein the pole piece ratio is the lithium ion battery anode material, acetylene black and PVDF in a mass ratio of 90:5:5; the metal lithium sheet is a counter electrode, the polypropylene microporous membrane Celgard 2400 is a diaphragm, and 1mol/L LiPF6/EC+DEC+DMC (volume ratio 1:1:1) is used as electrolyte to prepare the CR2025 button cell. Performing constant-current charge and discharge test on the battery by using a LAND battery test system, wherein the initial cyclic discharge specific capacity is 220mAh/g under the current density of 0.1C in a voltage window of 1.5-4.5V, and the capacity retention rate of 500 circles is 75%; at a current density of 1C, the specific capacity of cyclic discharge is 182mAh/g.
Comparative example 1
The comparative example provides a coated lithium ion battery cathode material comprising a lithium oxide core and a coating layer coating the lithium oxide core; the lithium oxide core is nickel cobalt lithium manganate (NCM 811) with an average particle size of 5 mu m; the coating layer is TiO with the mol ratio of 1:1 2 With Ti 4 O 7 Is a combination of (a); the mass ratio of the coating layer to the lithium oxide core was 0.05:1.
The preparation method of the coated lithium ion battery anode material comprises the following steps:
under the argon atmosphere condition, taking lithium oxide inner core as a matrix, utilizing tetraisopropyl titanate and water, and under the condition ofAtomic layer deposition is carried out on the surface of the substrate, and the ratio of Ti to O is controlled in the deposition process to ensure that TiO in the coating layer 2 With Ti 4 O 7 The molar ratio of the lithium ion battery anode material to the lithium ion battery anode material is 1:1.
Comparative example 2
The comparative example provides a coated lithium ion battery cathode material comprising a lithium oxide core and a coating layer coating the lithium oxide core; the lithium oxide core is nickel cobalt lithium manganate (NCM 811) with an average particle size of 5 mu m; the coating layer is Li with the mol ratio of 1:1 4 Ti 5 O 12 With Ti 4 O 7 Is a combination of (a); the mass ratio of the coating layer to the lithium oxide core was 0.05:1.
The preparation method of the coated lithium ion battery anode material comprises the following steps:
under the argon atmosphere condition, taking a lithium oxide inner core as a matrix, utilizing tetraisopropyl titanate, water and lithium tert-butoxide to perform atomic layer deposition on the surface of the matrix, and controlling the ratio of Li, ti and O in the deposition process to ensure that Li in the coating layer 4 Ti 5 O 12 With Ti 4 O 7 The molar ratio of the lithium ion battery anode material to the lithium ion battery anode material is 1:1.
Comparative example 3
The comparative example provides a coated lithium ion battery cathode material comprising a lithium oxide core and a coating layer coating the lithium oxide core; the lithium oxide core is nickel cobalt lithium manganate (NCM 811) with an average particle size of 5 mu m; the coating layer is Li with the mol ratio of 1:1 4 Ti 5 O 12 With TiO 2 Is a combination of (a); the mass ratio of the coating layer to the lithium oxide core was 0.05:1.
The preparation method of the coated lithium ion battery anode material comprises the following steps:
under the argon atmosphere condition, taking a lithium oxide inner core as a matrix, utilizing tetraisopropyl titanate, water and lithium tert-butoxide to perform atomic layer deposition on the surface of the matrix, and controlling the ratio of Li, ti and O in the deposition processExample Li in coating layer 4 Ti 5 O 12 With TiO 2 The molar ratio of the lithium ion battery anode material to the lithium ion battery anode material is 1:1.
Performance testing
Electrochemical performance tests are carried out on the coated lithium ion battery anode materials provided in the examples 1-16 and the comparative examples 1-3, wherein the pole piece ratio is that the mass ratio of the coated lithium ion battery anode materials to acetylene black to PVDF is 90:5:5; the metal lithium sheet is a counter electrode, the polypropylene microporous membrane Celgard 2400 is a diaphragm, and 1mol/L LiPF 6 And (3) preparing the CR2025 button cell by using the electrolyte solution with the ratio of (EC+DEC+DMC) (volume ratio of 1:1:1).
And performing constant current charge and discharge test on the prepared CR2025 button cell by adopting a LAND cell test system. Testing the specific capacity of the first cycle discharge and the capacity retention rate of 500 cycles under the current density of 0.1C in a voltage window of 2.5-4.5V; the first cycle discharge specific capacity was measured at a current density of 1C. The results obtained are shown in Table 1.
TABLE 1
As can be seen from examples 1-8 and examples 17-23, the coated lithium ion battery positive electrode material provided by the invention modifies the composite lithium oxide by simultaneously introducing lithium titanate, titanium dioxide and titanium dioxide, and improves the electronic conductivity and ionic conductivity of the material by utilizing the coordination effect between the three materials, thereby improving the specific capacity and the multiplying power performance of the material and prolonging the cycle life of the material.
As can be seen from a comparison of example 1 with examples 9-10, a too low or too high mass ratio of the coating layer to the lithium oxide core affects the electrochemical performance of the resulting coated lithium ion battery positive electrode material. When the quality of the coating layer is too low, an effective coating layer cannot be formed, so that the positive electrode material has the problem of capacity attenuation in the circulating process; when the quality of the coating layer is too high, the coating layer can obstruct the transmission of lithium ions between interfaces, and the specific discharge capacity of the positive electrode material is reduced.
As can be seen from a comparison of example 1 with examples 11-16, li 4 Ti 5 O 12 、TiO 2 With Ti 4 O 7 The molar ratio of (0.5-2) to (0.5-2) is in the preferred range, and in the molar ratio range, the three can cooperatively coat the lithium oxide core, so that the coating layer has good ionic conductivity and electronic conductivity, thereby having excellent electrochemical performance.
As is clear from a comparison of example 1 and comparative examples 1 to 3, the coating layer was formed by Li 4 Ti 5 O 12 、TiO 2 With Ti 4 O 7 Is modified by the synergistic effect of Li in the absence of 4 Ti 5 O 12 、TiO 2 With Ti 4 O 7 In any of these, no good effect of improving the electrochemical performance of the positive electrode material can be obtained.
In summary, the lithium titanate, the titanium dioxide and the titanium dioxide are simultaneously introduced to modify the composite lithium oxide, and the electronic conductivity and the ionic conductivity of the material are improved by utilizing the coordination effect among the three, so that the specific capacity and the multiplying power performance of the material are improved, and the cycle life of the material is prolonged. The lithium titanate has high ion conductivity and can improve the charge transfer of an anode/electrolyte interface; the lithium titanate and the titanium dioxide have obvious synergistic effect in the electrochemical reaction process, and can improve the electrochemical stability of the material; the titanium dioxide has the advantages of ultrahigh conductivity, good electrochemical stability, corrosion resistance and the like, and can improve the cycle life of the material. In addition, the three substances form a uniform coating layer, so that a physical barrier can be provided, the occurrence of side reactions is suppressed, the chemical attack of the electrolyte is prevented, and the dissolution of the transition metal is reduced. The three titanium-containing compounds have good coordination effect, and the composite positive electrode material obtained by the method has better conductivity, specific capacity, multiplying power characteristic, quick charge and discharge property and longer cycle life when being used as a positive electrode material of a lithium ion battery.
The foregoing is merely specific embodiments of the present invention, but the scope of the present invention is not limited thereto, and it should be apparent to those skilled in the art that any changes or substitutions that are within the technical scope of the present invention disclosed herein can be easily made by those skilled in the art, and fall within the scope of the present invention and the scope of the disclosure.
Claims (14)
1. The coated lithium ion battery anode material is characterized by comprising a lithium oxide inner core and a coating layer coating the lithium oxide inner core;
the coating layer comprises Li 4 Ti 5 O 12 、TiO 2 With Ti 4 O 7 Is a combination of (a) and (b).
2. The coated lithium ion battery positive electrode material of claim 1, wherein the chemical expression of the lithium oxide comprises Li x Ni a Co b Mn c M 1-a-b-c O 2 And/or Li x Fe d M` 1-d PO 4 Wherein M comprises any one or a combination of at least two of Mn, cr, co, ni, V, ti, al, ga, nb or Mg; m' comprises any one or a combination of at least two of Mn, cr, co, ni, V, ti, al, ga, nb or Mg; and a is more than or equal to 0 and less than or equal to 1, b is more than or equal to 0 and less than or equal to 1, c is more than or equal to 0 and less than or equal to 1, d is more than or equal to 0 and less than or equal to 1,0.4, and x is more than or equal to 1.5.
3. The coated lithium ion battery cathode material of claim 1, wherein the average particle size of the lithium oxide core is 1-20 μιη.
4. The coated lithium ion battery cathode material of claim 1, wherein the mass ratio of the coating layer to the lithium oxide core is (0.01-0.2): 1.
5. The coated lithium ion battery cathode material of claim 1, whichCharacterized in that Li in the coating layer 4 Ti 5 O 12 、TiO 2 With Ti 4 O 7 The molar ratio of (2) to (0.5-2).
6. A method for preparing the coated lithium ion battery cathode material according to any one of claims 1 to 5, wherein the preparation method comprises the following steps:
and (3) taking the lithium oxide inner core as a matrix, and depositing on the surface of the matrix by utilizing a deposition source to obtain the coated lithium ion battery anode material.
7. The method of claim 6, wherein the deposition source comprises a titanium source, an oxygen source, and a lithium source.
8. The method of claim 7, wherein the titanium source comprises any one or a combination of at least two of titanium tetrachloride, tetraisopropyl titanate, tetrabutyl titanate, or titanium dioxide.
9. The method of claim 7, wherein the oxygen source comprises water.
10. The method of claim 7, wherein the lithium source comprises any one or a combination of at least two of lithium tert-butoxide, lithium carbonate, lithium hydroxide, lithium acetate, or lithium oxide.
11. The method of claim 6, wherein the deposition method comprises any one or a combination of at least two of magnetron sputtering, electron beam evaporation, plasma enhanced chemical vapor deposition, or atomic layer deposition.
12. The method of claim 6, wherein the depositing is performed in a vacuum environment or a protective atmosphere.
13. The method of claim 12, wherein the protective atmosphere comprises any one or a combination of at least two of nitrogen, argon or helium.
14. A lithium ion battery, characterized in that the lithium ion battery comprises a coated lithium ion battery cathode material according to any one of claims 1-5.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101431154A (en) * | 2008-12-25 | 2009-05-13 | 成都中科来方能源科技有限公司 | Lithium titanate/C composite electrode material and method for producing the same |
| KR20120069398A (en) * | 2010-12-20 | 2012-06-28 | 삼성에스디아이 주식회사 | Positive active material, manufacturing method thereof and lithium battery containing the material |
| CN104979542A (en) * | 2014-04-11 | 2015-10-14 | 上海杉杉科技有限公司 | Modified lithium titanate composite material, preparation method and application thereof |
| CN105244488A (en) * | 2015-11-16 | 2016-01-13 | 湖南杉杉能源科技股份有限公司 | Compound cladding positive pole material of lithium ion battery and preparation method of compound cladding positive pole material |
-
2021
- 2021-11-30 CN CN202111442467.8A patent/CN114171733B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101431154A (en) * | 2008-12-25 | 2009-05-13 | 成都中科来方能源科技有限公司 | Lithium titanate/C composite electrode material and method for producing the same |
| KR20120069398A (en) * | 2010-12-20 | 2012-06-28 | 삼성에스디아이 주식회사 | Positive active material, manufacturing method thereof and lithium battery containing the material |
| CN104979542A (en) * | 2014-04-11 | 2015-10-14 | 上海杉杉科技有限公司 | Modified lithium titanate composite material, preparation method and application thereof |
| CN105244488A (en) * | 2015-11-16 | 2016-01-13 | 湖南杉杉能源科技股份有限公司 | Compound cladding positive pole material of lithium ion battery and preparation method of compound cladding positive pole material |
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