CN114171733A - Coated lithium ion battery anode material and preparation method and application thereof - Google Patents
Coated lithium ion battery anode material and preparation method and application thereof Download PDFInfo
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- CN114171733A CN114171733A CN202111442467.8A CN202111442467A CN114171733A CN 114171733 A CN114171733 A CN 114171733A CN 202111442467 A CN202111442467 A CN 202111442467A CN 114171733 A CN114171733 A CN 114171733A
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- lithium
- ion battery
- lithium ion
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- coating layer
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 104
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 103
- 239000010405 anode material Substances 0.000 title claims abstract description 59
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical group [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 claims abstract description 92
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 71
- 239000011247 coating layer Substances 0.000 claims abstract description 65
- 229910009848 Ti4O7 Inorganic materials 0.000 claims abstract description 40
- 239000010936 titanium Substances 0.000 claims abstract description 40
- 239000011248 coating agent Substances 0.000 claims abstract description 37
- 238000000576 coating method Methods 0.000 claims abstract description 37
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 37
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 37
- 229910009866 Ti5O12 Inorganic materials 0.000 claims abstract description 33
- 239000011159 matrix material Substances 0.000 claims abstract description 28
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910001947 lithium oxide Inorganic materials 0.000 claims abstract description 24
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 16
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 16
- 230000008021 deposition Effects 0.000 claims abstract description 10
- 229910002986 Li4Ti5O12 Inorganic materials 0.000 claims abstract description 9
- 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
- 239000007774 positive electrode material Substances 0.000 claims description 32
- 239000010406 cathode material Substances 0.000 claims description 26
- 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
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 21
- 238000000151 deposition Methods 0.000 claims description 16
- 239000004408 titanium dioxide Substances 0.000 claims description 16
- 239000000126 substance Substances 0.000 claims description 14
- 229910052782 aluminium Inorganic materials 0.000 claims description 13
- 229910052804 chromium Inorganic materials 0.000 claims description 13
- 229910052733 gallium Inorganic materials 0.000 claims description 13
- 229910052759 nickel Inorganic materials 0.000 claims description 13
- 229910052758 niobium Inorganic materials 0.000 claims description 13
- 239000002245 particle Substances 0.000 claims description 13
- 229910052720 vanadium Inorganic materials 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
- 229910052748 manganese 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 9
- 229910052749 magnesium Inorganic materials 0.000 claims description 9
- 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
- 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
- 229910005518 NiaCobMnc Inorganic materials 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 28
- 230000001351 cycling effect Effects 0.000 abstract 1
- 230000002441 reversible effect Effects 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 18
- HFCVPDYCRZVZDF-UHFFFAOYSA-N [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O Chemical group [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O HFCVPDYCRZVZDF-UHFFFAOYSA-N 0.000 description 16
- 125000004122 cyclic group Chemical group 0.000 description 14
- 239000003792 electrolyte Substances 0.000 description 14
- 239000011572 manganese Substances 0.000 description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 12
- 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
- 229910001290 LiPF6 Inorganic materials 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
- 239000002131 composite material Substances 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
- 238000005137 deposition process Methods 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 229910000572 Lithium Nickel Cobalt Manganese Oxide (NCM) Inorganic materials 0.000 description 5
- 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 5
- 230000000694 effects Effects 0.000 description 5
- 230000007797 corrosion Effects 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 239000007773 negative electrode material Substances 0.000 description 4
- 229910019142 PO4 Inorganic materials 0.000 description 3
- PFYQFCKUASLJLL-UHFFFAOYSA-N [Co].[Ni].[Li] Chemical compound [Co].[Ni].[Li] PFYQFCKUASLJLL-UHFFFAOYSA-N 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 150000002641 lithium Chemical class 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
- 239000000758 substrate Substances 0.000 description 3
- 239000011149 active material Substances 0.000 description 2
- UQZIWOQVLUASCR-UHFFFAOYSA-N alumane;titanium Chemical compound [AlH3].[Ti] UQZIWOQVLUASCR-UHFFFAOYSA-N 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000003487 electrochemical reaction Methods 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 239000012621 metal-organic framework Substances 0.000 description 2
- 239000000203 mixture Substances 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
- 230000002195 synergetic effect Effects 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
- 230000009471 action Effects 0.000 description 1
- 230000002238 attenuated effect Effects 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
- 230000015572 biosynthetic process 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
- 239000011651 chromium Substances 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
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 229910002102 lithium manganese oxide Inorganic materials 0.000 description 1
- VLXXBCXTUVRROQ-UHFFFAOYSA-N lithium;oxido-oxo-(oxomanganiooxy)manganese Chemical compound [Li+].[O-][Mn](=O)O[Mn]=O VLXXBCXTUVRROQ-UHFFFAOYSA-N 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 239000010955 niobium 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
- 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 and a preparation method and application thereof, wherein the coated lithium ion battery anode material comprises a lithium oxide core and a coating layer for coating the lithium oxide core; the coating layer comprises Li4Ti5O12、TiO2With Ti4O7Combinations 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 using a deposition system to obtain the coated lithium ion battery anode material. The anode material provided by the invention is prepared by coating Li on the inner core4Ti5O12、TiO2And Ti4O7The coating of the material with high ionic conductivity and high electronic conductivity is realized, and the stability of the whole structure of the material can be improvedThe method is promoted, so that the reversible specific capacity and the cycling stability of the material are improved, and the method has a good application prospect.
Description
Technical Field
The invention belongs to the technical field of battery materials, relates to a lithium ion battery anode material, and particularly relates to a coated lithium ion battery anode material as well as a preparation method and application thereof.
Background
With the rapid 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. The positive electrode material is a main factor for limiting the performance of the battery at present, and the performance of the positive electrode material accounts for nearly 40% of the cost of the lithium ion battery.
Currently, the positive electrode material includes lithium cobaltate, lithium nickel cobalt manganese oxide, lithium nickel cobalt aluminate, lithium manganese oxide or lithium iron phosphate, but the above materials all have respective defects. For example, lithium cobaltate is expensive, has poor overcharge resistance, and has limited capacity exertion at low voltage; the lithium nickel cobalt manganese oxide or lithium nickel cobalt aluminate ternary material has the problems of low compaction density, poor compatibility with electrolyte, gas expansion and the like; the high-temperature cycle and high-temperature storage performance of lithium manganate are poor; 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 anode 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 positive electrode material, which comprises: the positive electrode material is uniformly mixed into a solution containing a template agent, an organic solvent, a ligand and an organic titanium salt, then the uniformly mixed solution is transferred into a high-pressure reaction kettle, under the action of the template agent, the organic metal salt and the ligand are self-assembled into a metal organic framework material under high temperature and high pressure, and the metal organic framework material is uniformly coated on the surface of the positive electrode material. And carrying out suction filtration, drying and grinding on the obtained product, and then calcining to obtain the porous titanium dioxide coated lithium ion battery anode material.
CN 108767221A discloses a modified lithium battery anode material, a preparation method and a lithium ion battery, wherein the modified lithium battery anode material comprises an anode material and at least one part of a coating layer coated on the surface of the anode material, and the coating layer is composed of a titanium-aluminum composite oxide. The preparation method comprises the following steps: and mixing the positive electrode material and the titanium-aluminum composite oxide, performing ball milling, and sintering to obtain the modified lithium battery positive electrode material. The gram volume and the stability of the material are improved through coating.
CN 108615861a discloses a modified lithium ion battery cathode material, which comprises a lithium ion battery cathode substrate and a coating layer applied on the cathode substrate, wherein the coating layer comprises a high temperature stability material and an electrochemical active material. The lithium ion battery anode material is obtained by taking the combination of a high-temperature stable material and an electrochemical active material as a target material to be sputtered on a lithium ion battery anode substrate by a magnetron sputtering technology to form a coating layer.
The technical scheme reports the coating modification of the cathode material, but the coating mode and the selection of the coating still have room for improvement, and how to obtain more uniform coating and select a proper coating is a technical problem to be solved in the field.
Disclosure of Invention
The invention aims to provide a coated lithium ion battery anode material and a preparation method and application thereof4Ti5O12、TiO2With Ti4O7The high ionic conductance and high electronic conductance materials are coated together, and the coated lithium ion battery anode material with high conductivity, high specific capacity, high rate characteristic, quick charge and discharge and long cycle life is obtained.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides a coated lithium ion battery cathode material, which comprises a lithium oxide core and a coating layer for coating the lithium oxide core;
the coating layer comprises Li4Ti5O12、TiO2With Ti4O7Combinations of (a) and (b).
The invention adopts Li4Ti5O12、TiO2With Ti4O7Coating modification of lithium oxide, Li4Ti5O12The ionic conductivity is high, and the charge transfer of the interface of the positive electrode and the electrolyte can be improved; li4Ti5O12With TiO2The material has obvious synergistic effect in the electrochemical reaction process, and can improve the electrochemical stability of the material; ti4O7The material has the advantages of ultrahigh conductivity, good electrochemical stability and corrosion resistance and the like, and can prolong the cycle life of the material. The combination of the three titanium-containing compounds has good matching effect, and the composition is modified by matching the three substancesWhen the composite cathode material obtained by the invention is used as a cathode material of a lithium ion battery, the composite cathode material has better conductivity, specific capacity, rate characteristic, quick charge and discharge property and longer cycle life.
Furthermore, Li4Ti5O12、TiO2With Ti4O7The formation of a uniform coating layer can provide a physical barrier, inhibit the occurrence of side reactions, prevent chemical corrosion of the electrolyte, and mitigate the dissolution of transition metals.
Preferably, the chemical expression of the lithium oxide includes LixNiaCobMncM1-a-b-cO2And/or LixFedM`1- dPO4Wherein, M comprises any one or the combination of at least two of Mn, Cr, Co, Ni, V, Ti, Al, Ga, Nb or Mg; m' comprises any one or the 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, and x is more than or equal to 0.4 and less than or equal to 1.5.
The chemical expression of the lithium oxide of the present invention is LixNiaCobMncM1-a-b-cO2When M includes 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 combinations of Mn and Cr, Co and Ni, V and Ti, Al and Ga, Nb and Mg, Mn, Cr and Ni, Co, V, Ti and Al, Ga, Nb and Mg, or Mn, Cr, Co, Ni, V, Ti, Al, Ga, Nb and Mg.
The chemical expression of the lithium oxide of the present invention is LixFedM`1-dPO4When M' includes any one or a combination of at least two of Mn, Cr, Co, Ni, V, Ti, Al, Ga, Nb, or Mg, typical but not 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, 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, or combinations of Mn, Cr, Co, Ni, V, Ti, Al, Ga, Nb, and MgA combination of Mg.
In the chemical formula of the lithium oxide of 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 values not recited in the numerical range are also applicable.
In the chemical formula of the lithium oxide of 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 values not recited in the numerical range are also applicable.
In the chemical formula of the lithium oxide of 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 values not recited in the numerical range are also applicable.
In the chemical formula of the lithium oxide of 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 values not recited in the numerical range are also applicable.
In the chemical formula of the lithium oxide of 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 values not recited in the numerical range are also applicable.
Preferably, the lithium oxide core has an average particle size of 1 to 20 μm, and may be, for example, 1 μm, 3 μm, 5 μm, 8 μm, 10 μm, 12 μm, 15 μm, 16 μm, 18 μm or 20 μm, but is not limited to the recited values, and other values not recited in the numerical range are also applicable.
Preferably, the mass ratio of the coating layer to the lithium oxide core is (0.01-0.2):1, and 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, and other values not recited within the numerical range are equally applicable.
Preferably, Li in the coating layer4Ti5O12、TiO2With Ti4O7The molar ratio of (1: 1:1, 0) to (0.5-2) is, for example, 1:1:1, 05:0.5:1, 0.5:1:1, 0.5:2:1, 1:0.5:0.5, 1:1:0.5, 1:2:0.5, 2:0.5:1, 2:2:0.5 or 2:2:1, but not limited to the values listed, other values not listed within the numerical range are equally applicable.
In a second aspect, the present invention provides a preparation method of the coated lithium ion battery cathode material according to the first aspect, where the preparation method includes the following steps:
and taking the lithium oxide core as a matrix, and depositing on the surface of the matrix by using 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, typical but non-limiting combinations include titanium tetrachloride in combination with tetraisopropyl titanate, tetraisopropyl titanate in combination with tetrabutyl titanate, tetrabutyl titanate in combination with titanium dioxide, titanium tetrachloride, tetraisopropyl titanate in combination with tetrabutyl titanate, tetraisopropyl titanate, tetrabutyl titanate in combination with titanium dioxide, or titanium tetrachloride, tetraisopropyl titanate, tetrabutyl titanate in combination with 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, typical but non-limiting combinations include a combination of lithium tert-butoxide with lithium carbonate, a combination of lithium carbonate with lithium hydroxide, a combination of lithium acetate with lithium oxide, a combination of lithium tert-butoxide, lithium carbonate with lithium hydroxide, lithium acetate with lithium oxide, or a combination of lithium tert-butoxide, lithium carbonate, lithium hydroxide, lithium acetate with lithium oxide.
Preferably, 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.
The deposition method provided by the invention is a conventional method in the field as long as deposition can be realized, the specific parameters in the deposition method are not further limited, and the deposition method can be reasonably adjusted by a person skilled in the art according to actual needs.
The invention converts the composition in the deposition layer into Li by depositing a titanium source, an oxygen source and a lithium source4Ti5O12、 TiO2With Ti4O7Then, Li4Ti5O12、TiO2With Ti4O7The molar ratio of (1) to (2) to (0.5-2).
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, typical but non-limiting combinations include nitrogen and argon, argon and helium, nitrogen and helium, or nitrogen, argon and helium.
In a third aspect, the invention provides a lithium ion battery, which comprises 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 suboxide are introduced to modify the composite lithium oxide, and the coordination of the lithium titanate, the titanium dioxide and the titanium suboxide improves the electronic conductivity and the ionic conductivity of the material, so that the specific capacity and the rate capability of the material are improved, and the cycle life of the material is prolonged.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
The embodiment provides a coated lithium ion battery anode material, which comprises a lithium oxide core and a coating layer for coating the lithium oxide core;the lithium oxide core is nickel cobalt lithium manganate (NCM811), and the average particle size is 5 mu m; the coating layer is Li with a molar ratio of 1:1:14Ti5O12、TiO2With Ti4O7A combination of (1); the mass ratio of the coating 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 condition of argon atmosphere, taking a lithium oxide core as a matrix, performing atomic layer deposition on the surface of the matrix by using tetraisopropyl titanate, water and lithium tert-butoxide, and controlling the proportion of Li, Ti and O in the deposition process to ensure that Li in a coating layer4Ti5O12、TiO2With Ti4O7The molar ratio of the positive electrode material to the negative electrode material is 1:1:1, and the coated lithium ion battery positive electrode material is obtained.
Example 2
The embodiment provides a coated lithium ion battery anode material, which comprises a lithium oxide core and a coating layer for coating the lithium oxide core; the lithium oxide core is nickel cobalt lithium manganate (NCM811), and the average particle size is 3 mu m; the coating layer is Li with a molar ratio of 0.8:0.5:14Ti5O12、TiO2With Ti4O7A combination of (1); the mass ratio of the coating 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 core as a matrix, utilizing titanium tetrachloride, water and lithium acetate to carry out atomic layer deposition on the surface of the matrix, and controlling the proportion of Li, Ti and O in the deposition process to ensure that Li in a coating layer4Ti5O12、TiO2With Ti4O7The molar ratio of (A) to (B) is 0.8:0.5:1, and the coated lithium ion battery cathode material is obtained.
Example 3
The present embodiment provides a coated lithium ion battery cathode material, which includes a lithium oxide core to form a lithium ion battery cathode materialAnd a coating layer coating the lithium oxide core; the lithium oxide core is nickel cobalt lithium manganate (NCM811), and the average particle size is 5 mu m; the coating layer is Li with the molar ratio of 1:0.8:1.14Ti5O12、TiO2With Ti4O7A combination of (1); the mass ratio of the coating 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 condition of argon atmosphere, taking a lithium oxide inner core as a matrix, utilizing tetraisopropyl titanate, water and lithium hydroxide to carry out atomic layer deposition on the surface of the matrix, and controlling the proportion of Li, Ti and O in the deposition process to ensure that Li in a coating layer4Ti5O12、TiO2With Ti4O7The molar ratio of (1: 0.8: 1.1) to obtain the coated lithium ion battery cathode material.
Example 4
The embodiment provides a coated lithium ion battery anode material, which comprises a lithium oxide core and a coating layer for coating the lithium oxide core; the lithium oxide core is nickel cobalt lithium manganate (NCM811), and the average particle size is 10 mu m; the coating layer is Li with a molar ratio of 2:0.5:14Ti5O12、TiO2With Ti4O7A combination of (1); the mass ratio of the coating 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 condition of argon atmosphere, taking a lithium oxide inner core as a matrix, and performing electron beam evaporation on the surface of the matrix by using tetraisopropyl titanate, water and lithium acetate, wherein the proportion of Li, Ti and O is controlled in the electron beam evaporation process to ensure that Li in a coating layer4Ti5O12、TiO2With Ti4O7The molar ratio of (1) to (2: 0.5: 1) to obtain the coated lithium ion battery anode material.
Example 5
The embodiment provides a coated lithium ion battery anode material, andthe coated lithium ion battery positive electrode material comprises a lithium oxide core and a coating layer for coating the lithium oxide core; the lithium oxide core is nickel cobalt lithium manganate (NCM811), and the average particle size is 1 mu m; the coating layer is Li with a molar ratio of 0.5:0.5:14Ti5O12、TiO2With Ti4O7A combination of (1); the mass ratio of the coating 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 condition of argon atmosphere, taking a lithium oxide core as a matrix, performing magnetron sputtering on the surface of the matrix by using titanium dioxide, water and lithium oxide, and controlling the proportion of Li, Ti and O in the magnetron sputtering process to ensure that Li in a coating layer4Ti5O12、TiO2With Ti4O7The molar ratio of (A) to (B) is 0.5:0.5:1, and the coated lithium ion battery cathode material is obtained.
Example 6
The embodiment provides a coated lithium ion battery anode material, which comprises a lithium oxide core and a coating layer for coating the lithium oxide core; the lithium oxide core is nickel cobalt lithium manganate (NCM811), and the average particle size is 2 mu m; the coating layer is Li with a molar ratio of 2:1:24Ti5O12、TiO2With Ti4O7A combination of (1); the mass ratio of the coating 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 condition of argon atmosphere, taking a lithium oxide inner core as a matrix, and performing plasma enhanced chemical vapor deposition on the surface of the matrix by using titanium dioxide, water and lithium oxide, wherein the proportion of Li, Ti and O is controlled in the process of plasma enhanced chemical vapor deposition to ensure that Li in a coating layer4Ti5O12、TiO2With Ti4O7The molar ratio of the positive electrode material to the negative electrode material is 2:1:2, and the coated lithium ion battery positive electrode material is obtained.
Example 7
The embodiment provides a coated lithium ion battery anode material, which comprises a lithium oxide core and a coating layer for coating the lithium oxide core; the lithium oxide core is nickel cobalt lithium manganate (NCM811), and the average particle size is 20 mu m; the coating layer is Li with a molar ratio of 1:1:0.54Ti5O12、TiO2With Ti4O7A combination of (1); the mass ratio of the coating 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 condition of argon atmosphere, taking a lithium oxide core as a matrix, utilizing titanium tetrachloride, water and lithium carbonate to carry out atomic layer deposition on the surface of the matrix, and controlling the proportion of Li, Ti and O in the deposition process to ensure that Li in a coating layer4Ti5O12、TiO2With Ti4O7The molar ratio of the positive electrode material to the negative electrode material is 1:1:0.5, and the coated lithium ion battery positive electrode material is obtained.
Example 8
The embodiment provides a coated lithium ion battery anode material, which comprises a lithium oxide core and a coating layer for coating the lithium oxide core; the lithium oxide core is nickel cobalt lithium manganate (NCM811), and the average particle size is 10 mu m; the coating layer is Li with a molar ratio of 0.8:0.5:14Ti5O12、TiO2With Ti4O7A combination of (1); the mass ratio of the coating 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 condition of argon atmosphere, taking a lithium oxide core as a matrix, performing magnetron sputtering on the surface of the matrix by using tetrabutyl titanate, water and lithium hydroxide, and controlling the proportion of Li, Ti and O in the magnetron sputtering process to ensure that Li in a coating layer4Ti5O12、TiO2With Ti4O7The molar ratio of (A) to (B) is 0.8:0.5:1, and the coated lithium ion battery cathode material is obtained.
Example 9
This example provides a coated lithium ion battery positive electrode material, which is the same as example 1 except that the mass ratio of the coating layer to the lithium oxide core is 0.005: 1.
Example 10
This example provides a coated lithium ion battery cathode material, which is the same as example 1 except that the mass ratio of the coating layer to the lithium oxide core is 0.3: 1.
Example 11
This example provides a coated lithium ion battery cathode material, except Li in the coating layer4Ti5O12、 TiO2With Ti4O7The molar ratio of (A) to (B) was 0.2:1:1, and the rest was the same as in example 1.
Example 12
This example provides a coated lithium ion battery cathode material, except Li in the coating layer4Ti5O12、 TiO2With Ti4O7The molar ratio of (A) to (B) was 1:0.2:1, and the rest was the same as in example 1.
Example 13
This example provides a coated lithium ion battery cathode material, except Li in the coating layer4Ti5O12、 TiO2With Ti4O7The molar ratio of (1: 1: 0.2) was the same as in example 1.
Example 14
This example provides a coated lithium ion battery cathode material, except Li in the coating layer4Ti5O12、 TiO2With Ti4O7The molar ratio of (A) to (B) was 4.5:1:1, and the rest was the same as in example 1.
Example 15
This example provides a coated lithium ion battery cathode material, except Li in the coating layer4Ti5O12、 TiO2With Ti4O7The molar ratio of (A) to (B) was 1:4.5:1, and the rest was the same as in example 1.
Example 16
This example provides a coated lithium ion battery cathode material, except Li in the coating layer4Ti5O12、 TiO2With Ti4O7The molar ratio of (1: 1: 4.5) was the same as in example 1.
Example 17
This example provides a coated lithium ion battery positive electrode material, which is the same as that of example 1 except that lithium nickel cobalt manganese oxide (NCM811) is replaced with lithium nickel cobalt aluminate (NCA622) of equal mass.
Carrying out electrochemical performance test on the obtained coated lithium ion battery anode material, wherein the proportion of pole pieces is that the lithium ion battery anode material, the acetylene black and the PVDF are in a mass ratio of 90:5: 5; the metal lithium sheet is used as a counter electrode, the polypropylene microporous membrane Celgard 2400 is used as a diaphragm, and 1mol/L LiPF6/EC + DEC + DMC (volume ratio is 1:1:1) is used as electrolyte to prepare the CR2025 type button cell. Performing constant-current charge and discharge test on the battery by adopting an LAND battery test system, wherein the first cyclic discharge specific capacity is 207mAh/g and the capacity retention rate is 80% after 500 cycles under the voltage window of 2.5-4.2V and the current density of 0.1C; the specific cyclic discharge capacity is 168mAh/g under the current density of 1C.
Example 18
This example provides a coated lithium ion battery positive electrode material, which is the same as that of example 1 except that nickel cobalt lithium manganate (NCM811) is replaced by nickel cobalt lithium manganate (NCM622) of equal mass.
Carrying out electrochemical performance test on the obtained coated lithium ion battery anode material, wherein the proportion of pole pieces is that the lithium ion battery anode material, the acetylene black and the PVDF are in a mass ratio of 90:5: 5; the metal lithium sheet is used as a counter electrode, the polypropylene microporous membrane Celgard 2400 is used as a diaphragm, and 1mol/L LiPF6/EC + DEC + DMC (volume ratio is 1:1:1) is used as electrolyte to prepare the CR2025 type button cell. Performing constant-current charge and discharge test on the battery by adopting an LAND battery test system, wherein the first cyclic discharge specific capacity is 211mAh/g and the capacity retention rate is 86% after 500 cycles under the voltage window of 2.5-4.2V and the current density of 0.1C; the specific cyclic discharge capacity is 168mAh/g under the current density of 1C.
Example 19
This example provides a coated lithium ion battery positive electrode material, which is the same as that of example 1 except that lithium nickel cobalt manganese oxide (NCM811) was replaced with lithium nickelate of equal mass.
Carrying out electrochemical performance test on the obtained coated lithium ion battery anode material, wherein the proportion of pole pieces is that the lithium ion battery anode material, the acetylene black and the PVDF are in a mass ratio of 90:5: 5; the metal lithium sheet is used as a counter electrode, the polypropylene microporous membrane Celgard 2400 is used as a diaphragm, and 1mol/L LiPF6/EC + DEC + DMC (volume ratio is 1:1:1) is used as electrolyte to prepare the CR2025 type button cell. Performing constant-current charge and discharge test on the battery by adopting an LAND battery test system, wherein the first cyclic discharge specific capacity is 195mAh/g and the capacity retention rate is 87% after 500 cycles under the voltage window of 2.5-4.2V and the current density of 0.1C; the specific cyclic discharge capacity is 165mAh/g under the current density of 1C.
Example 20
This example provides a coated lithium ion battery cathode material, which is the same as that of example 1 except that lithium nickel cobalt manganese oxide (NCM811) is replaced with lithium iron phosphate of equal mass.
Carrying out electrochemical performance test on the obtained coated lithium ion battery anode material, wherein the proportion of pole pieces is that the lithium ion battery anode material, the acetylene black and the PVDF are in a mass ratio of 90:5: 5; the metal lithium sheet is used as a counter electrode, the polypropylene microporous membrane Celgard 2400 is used as a diaphragm, and 1mol/L LiPF6/EC + DEC + DMC (volume ratio is 1:1:1) is used as electrolyte to prepare the CR2025 type button cell. Performing constant-current charge and discharge test on the battery by adopting an LAND battery test system, wherein the first cyclic discharge specific capacity is 170mAh/g and the capacity retention rate is 89% after 500 cycles under the voltage window of 2.5-4.2V and the current density of 0.1C; the specific capacity of the cyclic discharge is 155mAh/g under the current density of 1C.
Example 21
This example provides a coated lithium ion battery cathode material, except that nickel cobalt lithium manganate (NCM811) is replaced by Li with equal mass1.2Ni0.2Ti0.6O2Otherwise, the same procedure as in example 1 was repeated.
Carrying out electrochemical performance test on the obtained coated lithium ion battery anode material, wherein the proportion of pole pieces is that the lithium ion battery anode material, the acetylene black and the PVDF are in a mass ratio of 90:5: 5; the metal lithium sheet is used as a counter electrode, the polypropylene microporous membrane Celgard 2400 is used as a diaphragm, and 1mol/L LiPF6/EC + DEC + DMC (volume ratio is 1:1:1) is used as electrolyte to prepare the CR2025 type button cell. Performing constant-current charge and discharge test on the battery by using an LAND battery test system, wherein the first cyclic discharge specific capacity is 250mAh/g and the capacity retention rate is 76% after 500 cycles under the voltage window of 1.5-4.5V and the current density of 0.1C; the specific cyclic discharge capacity is 192mAh/g under the current density of 1C.
Example 22
The embodiment provides a coated lithium ion battery cathode material, which is obtained by replacing nickel cobalt lithium manganate (NCM811) with LiMn with equal mass0.75Fe0.25PO4Otherwise, the same procedure as in example 1 was repeated.
Carrying out electrochemical performance test on the obtained coated lithium ion battery anode material, wherein the proportion of pole pieces is that the lithium ion battery anode material, the acetylene black and the PVDF are in a mass ratio of 90:5: 5; the metal lithium sheet is used as a counter electrode, the polypropylene microporous membrane Celgard 2400 is used as a diaphragm, and 1mol/L LiPF6/EC + DEC + DMC (volume ratio is 1:1:1) is used as electrolyte to prepare the CR2025 type button cell. Performing constant-current charge and discharge test on the battery by adopting an LAND battery test system, wherein the first cyclic discharge specific capacity is 165mAh/g and the capacity retention rate is 83% after 500 cycles under the voltage window of 2.5-4.2V and the current density of 0.1C; the specific cyclic discharge capacity is 142mAh/g under the current density of 1C.
Example 23
This example provides a coated lithium ion battery cathode material, except that nickel cobalt lithium manganate (NCM811) is replaced by Li with equal mass1.2Mn0.2Ti0.6O2Otherwise, the same procedure as in example 1 was repeated.
Carrying out electrochemical performance test on the obtained coated lithium ion battery anode material, wherein the proportion of pole pieces is that the lithium ion battery anode material, the acetylene black and the PVDF are in a mass ratio of 90:5: 5; the metal lithium sheet is used as a counter electrode, the polypropylene microporous membrane Celgard 2400 is used as a diaphragm, and 1mol/L LiPF6/EC + DEC + DMC (volume ratio is 1:1:1) is used as electrolyte to prepare the CR2025 type button cell. Performing constant-current charge and discharge test on the battery by using an LAND battery test system, wherein the first cyclic discharge specific capacity is 220mAh/g and the capacity retention rate is 75% after 500 cycles under the voltage window of 1.5-4.5V and the current density of 0.1C; the specific capacity of the cyclic discharge is 182mAh/g under the current density of 1C.
Comparative example 1
The present comparative example provides a coated lithium ion battery positive electrode material comprising a lithium oxide core and a coating layer coating the lithium oxide core; the lithium oxide core is nickel cobalt lithium manganate (NCM811), and the average particle size is 5 mu m; the coating layer is TiO with the molar ratio of 1:12With Ti4O7A combination of (1); the mass ratio of the coating 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 condition of argon atmosphere, taking a lithium oxide core as a matrix, utilizing tetraisopropyl titanate and water to perform atomic layer deposition on the surface of the matrix, and controlling the ratio of Ti to O in the deposition process to ensure that TiO in a coating layer2With Ti4O7The molar ratio of (A) to (B) is 1:1, and the coated lithium ion battery anode material is obtained.
Comparative example 2
The present comparative example provides a coated lithium ion battery positive electrode material comprising a lithium oxide core and a coating layer coating the lithium oxide core; the lithium oxide core is nickel cobalt lithium manganate (NCM811), and the average particle size is 5 mu m; the coating layer is Li with a molar ratio of 1:14Ti5O12With Ti4O7A combination of (1); the mass ratio of the coating 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 condition of argon atmosphere, taking a lithium oxide core as a matrix, performing atomic layer deposition on the surface of the matrix by using tetraisopropyl titanate, water and lithium tert-butoxide, and controlling the proportion of Li, Ti and O in the deposition process to ensure that Li in a coating layer4Ti5O12With Ti4O7The molar ratio of (A) to (B) is 1:1, and the coated lithium ion battery anode material is obtained.
Comparative example 3
The present comparative example provides a coated lithium ion battery positive electrode material comprising a lithium oxide core and a coating layer coating the lithium oxide core; the lithium oxide core is nickel cobalt lithium manganate (NCM811), and the average particle size is 5 mu m; the coating layer is Li with a molar ratio of 1:14Ti5O12With TiO2A combination of (1); the mass ratio of the coating 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 condition of argon atmosphere, taking a lithium oxide core as a matrix, performing atomic layer deposition on the surface of the matrix by using tetraisopropyl titanate, water and lithium tert-butoxide, and controlling the proportion of Li, Ti and O in the deposition process to ensure that Li in a coating layer4Ti5O12With TiO2The molar ratio of (A) to (B) is 1:1, and the coated lithium ion battery anode material is obtained.
Performance testing
Carrying out electrochemical performance test on the coated lithium ion battery anode materials provided by the embodiments 1-16 and the comparative examples 1-3, wherein the mass ratio of the anode material of the coated lithium ion battery to the acetylene black to the PVDF is 90:5: 5; a metal lithium sheet is used as a counter electrode, a polypropylene microporous membrane Celgard 2400 is used as a diaphragm, and 1mol/L LiPF6Preparing a CR2025 type button cell by using/EC + DEC + DMC (volume ratio of 1:1:1) as an electrolyte.
And (3) carrying out constant-current charge and discharge test on the prepared CR2025 type button battery by adopting an LAND battery test system. Testing the first cycle discharge specific capacity and the capacity retention rate of 500 cycles in a voltage window of 2.5-4.5V and a current density of 0.1C; the first cycle specific discharge capacity was determined at a current density of 1C. The results obtained are shown in table 1.
TABLE 1
As can be seen from examples 1 to 8 and examples 17 to 23, the coated lithium ion battery positive electrode material provided by the present invention modifies the composite lithium oxide by simultaneously introducing lithium titanate, titanium dioxide and titanium suboxide, and improves the electronic conductivity and ionic conductivity of the material by utilizing the cooperation effect of the lithium titanate, the titanium dioxide and the titanium suboxide, thereby improving the specific capacity and rate capability of the material, and prolonging the cycle life of the material.
From the comparison between example 1 and examples 9 to 10, it is clear that the electrochemical performance of the obtained coated lithium ion battery positive electrode material is affected by the mass ratio of the coating layer to the lithium oxide core being too low or too high. When the quality of the coating layer is too low, an effective coating layer cannot be formed, so that the capacity of the positive electrode material is attenuated in the circulation process; when the quality of the coating layer is too high, the coating layer can block the transmission of lithium ions between interfaces, and the specific discharge capacity of the cathode material is reduced.
From comparison of example 1 with examples 11 to 16, Li4Ti5O12、TiO2With Ti4O7The preferable range of the molar ratio of (0.5-2): (0.5-2): 0.5-2) exists, and in the molar ratio range, the three can be used for cooperatively coating 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 comparison of example 1 with comparative examples 1 to 3, the coating layer passes Li4Ti5O12、TiO2With Ti4O7When Li is absent, the modification effect is exerted synergistically4Ti5O12、TiO2With Ti4O7Any of these substances cannot provide a good effect of improving the electrochemical properties of the positive electrode material.
In conclusion, the lithium titanate, the titanium dioxide and the titanium suboxide are introduced to modify the composite lithium oxide, and the coordination of the lithium titanate, the titanium dioxide and the titanium suboxide improves the electronic conductivity and the ionic conductivity of the material, so that the specific capacity and the rate capability of the material are improved, and the cycle life of the material is prolonged. The lithium titanate has high ionic conductivity and can improve the charge transfer of a positive electrode/electrolyte interface; the lithium titanate and the titanium dioxide have obvious synergistic effect in the electrochemical reaction process, and the electrochemical stability of the material can be improved; the titanium dioxide has the advantages of ultrahigh conductivity, good electrochemical stability, corrosion resistance and the like, and can prolong the cycle life of the material. In addition, the three substances form a uniform coating layer, and can provide a physical barrier, inhibit the occurrence of side reactions, prevent the chemical corrosion of the electrolyte and reduce the dissolution of transition metals. The combination of the three titanium-containing compounds has good matching effect, and the composite anode material obtained by the invention has better conductivity, specific capacity, rate characteristic, quick charge and discharge property and longer cycle life when being used as the anode material of the lithium ion battery through matching modification of the three substances.
The above description is only for the specific embodiments of the present invention, but the scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the scope of the present invention and the disclosure.
Claims (10)
1. The coated lithium ion battery positive electrode material is characterized by comprising a lithium oxide core and a coating layer for coating the lithium oxide core;
the coating layer comprises Li4Ti5O12、TiO2With Ti4O7Combinations of (a) and (b).
2. The coated lithium ion battery positive electrode material according to claim 1, wherein the chemical expression of the lithium oxide includes LixNiaCobMncM1-a-b-cO2And/or LixFedM`1-dPO4Wherein, M comprises any one or the combination of at least two of Mn, Cr, Co, Ni, V, Ti, Al, Ga, Nb or Mg; m' comprises any one or the 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, and x is more than or equal to 0.4 and less than or equal to 1.5.
3. The coated lithium ion battery positive electrode material according to claim 1 or 2, wherein the average particle diameter of the lithium oxide core is 1 to 20 μm;
preferably, the mass ratio of the coating layer to the lithium oxide core is (0.01-0.2): 1.
4. The coated lithium ion battery positive electrode material according to any one of claims 1 to 3, wherein Li in the coating layer4Ti5O12、TiO2With Ti4O7The molar ratio of (0.5-2) to (0.5-2).
5. The preparation method of the coated lithium ion battery cathode material as claimed in any one of claims 1 to 4, characterized in that the preparation method comprises the following steps:
and taking the lithium oxide core as a matrix, and depositing on the surface of the matrix by using a deposition source to obtain the coated lithium ion battery anode material.
6. The method of claim 5, wherein the deposition source comprises a titanium source, an oxygen source, and a lithium source.
7. The production method according to claim 6, wherein the titanium source comprises any one of titanium tetrachloride, tetraisopropyl titanate, tetrabutyl titanate, or titanium dioxide, or a combination of at least two of them;
preferably, the oxygen source comprises water;
preferably, the lithium source comprises any one of lithium tert-butoxide, lithium carbonate, lithium hydroxide, lithium acetate or lithium oxide or a combination of at least two of them.
8. The method of any one of claims 5-7, wherein the 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.
9. The method according to any one of claims 5 to 8, wherein the deposition is performed in a vacuum environment or a protective atmosphere;
preferably, the gas used in the protective atmosphere comprises any one of nitrogen, argon or helium or a combination of at least two thereof.
10. A lithium ion battery, characterized in that the lithium ion battery comprises the coated lithium ion battery positive electrode material according to any one of claims 1 to 4.
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| 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 |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2801394C1 (en) * | 2023-06-02 | 2023-08-08 | федеральное государственное автономное образовательное учреждение высшего образования "Санкт-Петербургский политехнический университет Петра Великого" (ФГАОУ ВО "СПбПУ") | Method for modifying the cathode surface of a lithium-ion battery with a titanium oxide film |
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| CN114171733B (en) | 2024-02-13 |
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