CN106450217A - Method for modifying nickel cobalt lithium manganate ternary material - Google Patents
Method for modifying nickel cobalt lithium manganate ternary material Download PDFInfo
- Publication number
- CN106450217A CN106450217A CN201610978496.9A CN201610978496A CN106450217A CN 106450217 A CN106450217 A CN 106450217A CN 201610978496 A CN201610978496 A CN 201610978496A CN 106450217 A CN106450217 A CN 106450217A
- Authority
- CN
- China
- Prior art keywords
- lithium manganate
- carbon
- nickel
- ternary material
- cobalt
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000463 material Substances 0.000 title claims abstract description 137
- 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 title claims abstract description 60
- 238000000034 method Methods 0.000 title claims abstract description 38
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 53
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 44
- 239000011248 coating agent Substances 0.000 claims abstract description 29
- 238000000576 coating method Methods 0.000 claims abstract description 29
- 230000001681 protective effect Effects 0.000 claims abstract description 21
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 19
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000007789 gas Substances 0.000 claims description 69
- 230000008021 deposition Effects 0.000 claims description 47
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 39
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 25
- 238000010438 heat treatment Methods 0.000 claims description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 12
- 239000001569 carbon dioxide Substances 0.000 claims description 12
- 239000000126 substance Substances 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 239000010406 cathode material Substances 0.000 claims description 7
- 229910014336 LiNi1-x-yCoxMnyO2 Inorganic materials 0.000 claims description 6
- 229910014446 LiNi1−x-yCoxMnyO2 Inorganic materials 0.000 claims description 6
- 229910014825 LiNi1−x−yCoxMnyO2 Inorganic materials 0.000 claims description 6
- 229910052756 noble gas Inorganic materials 0.000 claims description 6
- 150000002835 noble gases Chemical class 0.000 claims description 6
- -1 ethylene, propylene Chemical group 0.000 claims description 5
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims description 4
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 4
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims description 4
- 230000004048 modification Effects 0.000 claims description 4
- 238000012986 modification Methods 0.000 claims description 4
- 150000001336 alkenes Chemical class 0.000 claims description 3
- 150000001345 alkine derivatives Chemical class 0.000 claims description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 2
- 230000007717 exclusion Effects 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 7
- 230000008901 benefit Effects 0.000 abstract description 5
- 238000009792 diffusion process Methods 0.000 abstract description 5
- 238000007740 vapor deposition Methods 0.000 abstract 2
- 238000002715 modification method Methods 0.000 abstract 1
- 238000000151 deposition Methods 0.000 description 42
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 32
- 239000010453 quartz Substances 0.000 description 32
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 32
- 229910052744 lithium Inorganic materials 0.000 description 24
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 23
- 239000003708 ampul Substances 0.000 description 22
- 229910052786 argon Inorganic materials 0.000 description 16
- 229960004424 carbon dioxide Drugs 0.000 description 12
- 150000001721 carbon Chemical class 0.000 description 11
- 230000000694 effects Effects 0.000 description 11
- 238000002360 preparation method Methods 0.000 description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 7
- 238000012360 testing method Methods 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 238000005253 cladding Methods 0.000 description 5
- 229910017052 cobalt Inorganic materials 0.000 description 4
- 239000010941 cobalt Substances 0.000 description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 4
- 238000005336 cracking Methods 0.000 description 4
- 238000005137 deposition process Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- OVAQODDUFGFVPR-UHFFFAOYSA-N lithium cobalt(2+) dioxido(dioxo)manganese Chemical compound [Li+].[Mn](=O)(=O)([O-])[O-].[Co+2] OVAQODDUFGFVPR-UHFFFAOYSA-N 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- 238000007086 side reaction Methods 0.000 description 4
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 description 3
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 description 3
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 3
- 239000010405 anode material Substances 0.000 description 3
- 125000002091 cationic group Chemical group 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 230000004044 response Effects 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- 229910000572 Lithium Nickel Cobalt Manganese Oxide (NCM) Inorganic materials 0.000 description 2
- QJXZFUFWYXMYEY-UHFFFAOYSA-N [C+4].[Mn](=O)(=O)([O-])[O-].[Li+].[Co+2].[Ni+2] Chemical class [C+4].[Mn](=O)(=O)([O-])[O-].[Li+].[Co+2].[Ni+2] QJXZFUFWYXMYEY-UHFFFAOYSA-N 0.000 description 2
- MOLYXOOGDFTUJT-UHFFFAOYSA-L [Li].[Mn](=O)(=O)(O)O.[Co] Chemical compound [Li].[Mn](=O)(=O)(O)O.[Co] MOLYXOOGDFTUJT-UHFFFAOYSA-L 0.000 description 2
- 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 2
- 230000004888 barrier function Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000002079 cooperative effect Effects 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
- 230000005518 electrochemistry Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 230000005536 Jahn Teller effect Effects 0.000 description 1
- 229910032387 LiCoO2 Inorganic materials 0.000 description 1
- 229910002993 LiMnO2 Inorganic materials 0.000 description 1
- 229910003005 LiNiO2 Inorganic materials 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- UAAWQXWGRFRTRQ-UHFFFAOYSA-N [Mn](=O)(=O)([O-])[O-].[Co+2].[Li+].[Ni+2].[Ni+2] Chemical compound [Mn](=O)(=O)([O-])[O-].[Co+2].[Li+].[Ni+2].[Ni+2] UAAWQXWGRFRTRQ-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000005030 aluminium foil Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000007767 bonding agent Substances 0.000 description 1
- 229910002090 carbon oxide Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- ZGDWHDKHJKZZIQ-UHFFFAOYSA-N cobalt nickel Chemical compound [Co].[Ni].[Ni].[Ni] ZGDWHDKHJKZZIQ-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 238000010998 test method Methods 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
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Composite Materials (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention provides a method for modifying a nickel cobalt lithium manganate ternary material, which comprises the following steps of carrying out vapor deposition on a nickel cobalt lithium manganate material under the conditions of a carbon source gas and a protective gas to obtain a carbon-coated modified nickel cobalt lithium manganate material. According to the invention, carbon is deposited on the surface of the nickel cobalt lithium manganate ternary material by a vapor deposition method, so that carbon coating is realized; the carbon coated by the nickel cobalt lithium manganate ternary material improves the first charge-discharge efficiency, improves the lithium ion diffusion coefficient and the electronic conductivity of the material, and improves the electrochemical performance of the NCM material. The modification method provided by the invention has the advantages of relatively simple equipment, few processes, controllable structure and higher battery capacity, cycle performance and rate capability of the material.
Description
Technical field
The present invention relates to technical field of lithium ion battery electrode, it is related to a kind of modification of cobalt nickel lithium manganate ternary material
Method is and in particular to a kind of coated modified carbon method of cobalt nickel lithium manganate ternary material.
Background technology
Lithium ion battery has that running voltage is high, specific energy is high, has extended cycle life, lightweight, white electric discharge less, memoryless effect
Should be with cost performance ratio, it has also become the field such as high power electric vehicle, artificial satellite, Aero-Space rechargeable type electricity
The main selecting object of source, portable type electronic product and the new forms of energy vehicles, is the current preferably new energy generally acknowledged in the world
Source automobile energy storage and out-put supply.Therefore lithium ion battery and its associated materials become the study hotspot of scientific research personnel.Just
Pole material is one of lithium ion battery core, decides the performance of lithium ion battery, and current limiting lithium ion power current
The maximum bottleneck of pond energy density, power density, cycle life and safety is positive electrode technology.
At present, anode material for lithium-ion batteries is studied with widely used as cobalt acid lithium material, lithium manganate material, phosphorus
Sour ferrum lithium material, ternary material etc..Wherein cobalt acid lithium is to realize the lithium ion cell positive of industrialization and commercial applications earliest
Material, but cobalt is scarce resource, expensive, there is certain pollution to environment；Although lithium nickelate theoretical specific capacity is high, close
Become difficult, the poor reproducibility of material；Although the raw material aboundresources of LiMn2O4, cheap, spinel lithium manganate capacity is low,
Easily there is Jahn-Teller effect in crystal structure, capacity attenuation is fast, and cycle performance is poor.Comprehensive cobalt acid lithium, lithium nickelate and mangaic acid
The performance of lithium, tri- kinds of transition metals of Ni, Co and Mn is combined and prepares lithium nickel cobalt manganese oxide, i.e. nickel cobalt again
LiMn2O4 ternary material (NCM), i.e. the ternary layered positive electrode of nickle cobalt lithium manganate, its chemical formula is LiNi1-x-yCoxMnyO2, bag
Include Ni-based ternary material, or claim nickelic ternary material (LiNi1-x-yCoxMnyO2(1-x-y≥0.5)).Due to tri- kinds of Ni, Co and Mn
The cooperative effect of element, combines LiCoO2, LiNiO2And LiMnO2The advantage of three kinds of anode material for lithium-ion batteries, its performance
It is better than any of the above one-component positive electrode, there is obvious cooperative effect.In this system, the chemical property of material and thing
Rationality can be different with the change of these three transition metal ratios, have that heat stability is good, energy density is high, high potential
Lower specific capacity is high and the low feature of cost of material is it is considered to be one of the most promising anode material for lithium-ion batteries.
Although lithium nickel cobalt manganese oxide tertiary cathode material has many advantages, such as above-mentioned.But due to cation mixing effect
Should and change during initial charge for the material surface micro structure, cause the first charge-discharge efficiency of ternary material not high；
And lithium ion diffusion coefficient and electronic conductivity is low so that the high rate performance of material is less desirable；Ternary material is in wide electricity
With organic bath, strong side reaction can occur in the range of pressure, increase impedance in charge and discharge process for the battery, reduce material
The defect such as chemical property.And at present ternary material is carried out with a big focus that coated modified carbon is current research it is possible to
Solve some problem above.And traditional high-temperature cracking method is carried out during carbon coating easily by the lithium nickelate in ternary material
Reduction, thus have impact on its electrical property.
Therefore, how to obtain a kind of method of modifying of more preferable cobalt nickel lithium manganate ternary material, improve its electrical property, become
For field Nei Ge production firm and line R＆D and production personnel's problem demanding prompt solution.
Content of the invention
In view of this, the technical problem to be solved in the present invention there are provided a kind of modification of cobalt nickel lithium manganate ternary material
Method, the coated modified carbon method of especially a kind of cobalt nickel lithium manganate ternary material, the nickel of the coated modified carbon of present invention preparation
Cobalt manganic acid lithium ternary material, has higher battery capacity, cycle performance and high rate performance.
The invention provides a kind of method of modifying of cobalt nickel lithium manganate ternary material, comprise the following steps：
A) under conditions of carbon-source gas and protective gas, by nickel-cobalt lithium manganate material after vapour deposition, obtain
The modified nickel-cobalt lithium manganate material of carbon coating.
Preferably, described carbon source includes one or more of alkane, alkene and alkynes.
Preferably, described carbon source includes one or more of methane, ethane, ethylene, propylene and acetylene；
Described protective gas includes one or more of carbon dioxide, nitrogen and noble gases.
Preferably, the speed that is passed through of described carbon-source gas is 20～100mL/min.
Preferably, the speed that is passed through of described protective gas is 30～150mL/min.
Preferably, the temperature of described vapour deposition is 500～1500 DEG C；
The time of described vapour deposition is 5～120min；
The heating rate of the heating process of described vapour deposition is 5～30 DEG C/min.
Preferably, the carbon coating amount of the modified nickel-cobalt lithium manganate material of described carbon coating is 3%～10%.
Preferably, also include before described vapour deposition, be passed through the step that protective gas excludes air；
Described protective gas is nitrogen and/or noble gases；
The speed that is passed through of described protective gas is 20～100mL/min；
The time that is passed through of described protective gas is 10～120min.
Preferably, described nickel-cobalt lithium manganate material is nickelic tertiary cathode material；
Shown in the chemical formula such as formula (II) of described nickelic tertiary cathode material,
LiNi1-x-yCoxMnyO2(II)；
Wherein, (1-x-y) >=0.5, x ＞ 0, y ＞ 0.
The invention provides a kind of lithium ion battery, described positive pole includes changing prepared by technique scheme any one
Property nickel-cobalt lithium manganate material.
The invention provides a kind of method of modifying of cobalt nickel lithium manganate ternary material, comprise the following steps, in carbon-source gas
Under conditions of protective gas, by nickel-cobalt lithium manganate material after vapour deposition, obtain the modified nickel cobalt mangaic acid of carbon coating
Lithium material.Compared with prior art, the present invention passes through vapour deposition process, deposits carbon on cobalt nickel lithium manganate ternary material surface, from
And achieving carbon coating, the present invention adopts better simply operation, under the auxiliary of protective gas, carries out carbon bag to ternary material
Cover, effectively solve the problems, such as that the lithium nickelate during traditional ternary material carbon coating is reduced it is achieved that carbon-coating is three
The cladding of first material surface；Cobalt nickel lithium manganate ternary material carbon coated is effectively reduced the mixing of lithium layer cationic, improves
First charge-discharge efficiency, improves lithium ion diffusion coefficient and the electronic conductivity of material；And reduce organic bath and electrode material
There is strong side reaction in material, reduce impedance in charge and discharge process for the battery, improve the chemical property of NCM material.This
The preparation method that invention provides, equipment is relatively easy, and operation is few, and carbon structure is controlled, and the nickel cobalt of the coated modified carbon prepared
LiMn2O4 ternary material, has higher battery capacity, cycle performance and high rate performance.Test result indicate that, prepared by the present invention
Coated modified carbon cobalt nickel lithium manganate ternary material preparation lithium battery 1C capacity be 33.6, circulation 50 times after, capacity remains to
Enough reach 96.2%.
Brief description
Fig. 1 prepares the device general flow chart of carbon coating cobalt nickel lithium manganate ternary material for vapour deposition process of the present invention.
Specific embodiment
In order to further appreciate that the present invention, with reference to embodiment, the preferred embodiments of the invention are described, but
It is it should be appreciated that these descriptions are simply to further illustrate the features and advantages of the present invention rather than to patent requirements of the present invention
Limit.
The all raw materials of the present invention, originate to it and are not particularly limited, commercially buying or according to people in the art
Conventional method preparation known to member.
The all raw materials of the present invention, are not particularly limited to its purity, present invention preferably employs analyzing pure or lithium ion battery
The conventional purity in field.
The invention provides a kind of method of modifying of cobalt nickel lithium manganate ternary material, comprise the following steps：
A) under conditions of carbon-source gas and protective gas, by nickel-cobalt lithium manganate material after vapour deposition, obtain
The modified nickel-cobalt lithium manganate material of carbon coating.
The present invention is not particularly limited to described nickel-cobalt lithium manganate material, with well known to those skilled in the art in making lithium
The NCM ternary material of ion battery positive pole, i.e. nickel-cobalt lithium manganate material, the chemical formula such as formula of described nickel-cobalt lithium manganate material
(I) shown in,
LiNi1-x-yCoxMnyO2(I)；
Wherein, x ＞ 0, y ＞ 0,1 ＞ 1-x-y ＞ 0.
The present invention is the performance improving ternary material as positive electrode, and described nickel-cobalt lithium manganate material is more preferably nickelic
Nickle cobalt lithium manganate tertiary cathode material (or claiming rich nickel cobalt nickel lithium manganate ternary material, Ni-based ternary material), described nickelic ternary
Shown in the chemical formula of positive electrode such as formula (II),
LiNi1-x-yCoxMnyO2(II)；
Wherein, (1-x-y) >=0.5, x ＞ 0, y ＞ 0.
Further, the span of described x preferably 0.1≤x≤0.2, more preferably 0.12≤x≤0.18, more preferably
For 0.14≤x≤0.16；The span of described y preferably 0.1≤y≤0.3, more preferably 0.13≤y≤0.27, more preferably
0.16≤y≤0.24, most preferably 0.19≤y≤0.21；The span of described 1-x-y is preferably 0.5≤1-x-y≤0.9, more
Preferably 0.6≤1-x-y≤0.9, most preferably 0.7≤1-x-y≤0.8.
The present invention is not particularly limited to described nickel-cobalt lithium manganate material other conditions, with well known to those skilled in the art
The normal condition of NCM ternary material, those skilled in the art can be according to practical condition, combining case and product
Performance is selected, and the present invention is the performance being further ensured that trielement composite material, and the particle diameter of described nickel-cobalt lithium manganate material is excellent
Elect 12～14 μm as, more preferably 12.3～13.7 μm, most preferably 12.5～13.5 μm.
The present invention is not particularly limited to the thickness degree of described carbon coating, with conventional cladding well known to those skilled in the art
Thickness, those skilled in the art can be selected according to practical condition, deposition conditions and properties of product, this
Bright employing gas phase deposition technology, can be by regulating and controlling the thickness degree of state modulator cladding.The cladding to described carbon coating for the present invention
Amount is not particularly limited, and with routine covering amount well known to those skilled in the art, those skilled in the art can be according to reality
The border condition of production, deposition conditions and properties of product are selected, and the present invention adopts gas phase deposition technology, can be joined by regulation and control
The covering amount of numerical control carbon coating, the covering amount of carbon coating of the present invention, that is, described carbon account for described modification nickle cobalt lithium manganate material
The percentage composition of material preferably 3%～10%, more preferably 4%～9%, more preferably 4%～9%, most preferably 6%～
7%.
The present invention passes through coated modified carbon nickel-cobalt lithium manganate material, is effectively reduced ternary material lithium layer cationic
Mixing, improves first charge-discharge efficiency, improves lithium ion diffusion coefficient and the electronic conductivity of material.And reduce so that Organic Electricity
There is strong side reaction in solution matter and electrode material, reduce impedance in charge and discharge process for the battery, improves the electrochemistry of material
Performance.
The present invention is not particularly limited to described carbon-source gas, with carbon-source gas well known to those skilled in the art,
Those skilled in the art can be selected according to practical condition, deposition conditions and properties of product and be adjusted, the present invention
Described carbon-source gas preferably include one or more of paraffin gas, olefin gas and alkynes gas, more preferably include methane,
One or more of ethane, ethylene, propylene and acetylene, more preferably methane, ethane, ethylene, propylene or acetylene, most preferably
Methane.Gas of the present invention is preferably gaseous state at normal temperatures.The present invention does not have to the speed that is passed through of described carbon-source gas
Have special restriction, those skilled in the art can be selected according to practical condition, deposition conditions and properties of product and
Adjustment, the present invention be improve deposition effect, control carbon structure formed, described carbon-source gas be passed through speed be preferably 20～
100mL/min, more preferably 30～90mL/min, more preferably 40～80mL/min, most preferably 50～70mL/min.
The present invention is not particularly limited to described protective gas, with protective gas well known to those skilled in the art is
Can, those skilled in the art can be selected according to practical condition, deposition conditions and properties of product and be adjusted, this
Bright for improve deposition effect, control carbon structure formed, prevent NCM ternary material to be reduced, described protective gas preferably includes
One or more of carbon dioxide, nitrogen and noble gases, more preferably carbon dioxide, nitrogen or argon, most preferably two
Carbonoxide.The present invention is not particularly limited to the speed that is passed through of described protective gas, and those skilled in the art can be according to reality
The border condition of production, deposition conditions and properties of product are selected and are adjusted, and the present invention is to improve deposition effect, controls carbon structure
Formed, prevent NCM ternary material to be reduced, the speed that is passed through of described protective gas is preferably 30～150mL/min, more preferably
For 50～130mL/min, more preferably 70～110mL/min, most preferably 80～100mL/min.
The present invention is not particularly limited to the temperature of described vapour deposition, with vapour deposition well known to those skilled in the art
Temperature, those skilled in the art can be selected according to practical condition, deposition conditions and properties of product and
Adjustment, the present invention is to improve deposition effect, controls carbon structure to be formed, prevents NCM ternary material to be reduced, described vapour deposition
Temperature is preferably 500～1500 DEG C, more preferably 700～1300 DEG C, most preferably 900～1100 DEG C.
The present invention was not particularly limited to the time of described vapour deposition, and those skilled in the art can be according to actual production
Situation, deposition conditions and properties of product are selected and are adjusted, and the present invention is to improve deposition effect, control carbon structure to be formed,
NCM ternary material is prevented to be reduced, the time of described vapour deposition is preferably 10～110min, more preferably 30～90min, more
It is preferably 40～80min, most preferably 50～70min.
The actual conditions of the heating process to described vapour deposition for the present invention is not particularly limited, with those skilled in the art
Known to vapour deposition heating process, those skilled in the art can according to practical condition, deposition conditions and
Properties of product are selected and are adjusted, and the present invention is to improve deposition effect, control carbon structure to be formed, prevent NCM ternary material quilt
Reduction, the heating rate of the heating process of described vapour deposition is preferably 5～30 DEG C/min, more preferably 10～25 DEG C/min,
Most preferably 15～20 DEG C/min.
The present invention is to ensure deposition effect, improves the chemical property of modified ternary material, preferably in described vapour deposition
Also include before, be passed through the step that gas excludes air.The present invention is not particularly limited to described gas, with people in the art
Protective gas known to member, those skilled in the art can be according to practical condition, deposition conditions and product
Can be selected and be adjusted, gas of the present invention preferably nitrogen and/or noble gases, more preferably nitrogen and/or argon,
Most preferably argon.The present invention is not particularly limited to the speed that is passed through of described gas, and those skilled in the art can be according to reality
The border condition of production, deposition conditions and properties of product are selected and are adjusted, described gas be passed through speed be preferably 20～
100mL/min, more preferably 30～90mL/min, more preferably 40～80mL/min, most preferably 50～70mL/min.This
The bright time that is passed through to described gas is not particularly limited, and those skilled in the art can be according to practical condition, deposition feelings
Condition and properties of product are selected and are adjusted, and the present invention is to improve deposition effect, control carbon structure to be formed, prevent NCM ternary
Material is reduced, described gas be passed through the time be preferably 10～120min, more preferably 30～110min, more preferably 50～
90min, most preferably 60～80min.
Present invention also offers a kind of lithium ion battery, described positive pole is included prepared by above-mentioned any one technical scheme
Modified nickel-cobalt lithium manganate material.
The present invention is not particularly limited to the preparation method of described positive pole, with NCM lithium well known to those skilled in the art from
The conventional preparation method of sub- anode, modified NCM tertiary cathode material that the present invention is preferably prepared by said method, leads
Prepare slurry after electric agent and binding agent mix and blend, and slurry is coated in aluminum foil current collector, drying obtains lithium after cutting
Ion battery positive electrode pole piece.
Above-mentioned steps of the present invention pass through vapour deposition process, deposit carbon on cobalt nickel lithium manganate ternary material surface, thus realizing
Carbon coating, the present invention adopts better simply operation, under the auxiliary of protective gas, ternary material is carried out with carbon coating, special
It is not to preferably use carbon-source gas and carbon dioxide to carry out, for source of the gas, the carbon coating that chemical vapor deposition carries out ternary material, pass through
Control flow, vapour deposition temperature and the retention time of carbon dioxide and methane gas, make carbon-coating successfully be coated on ternary material
Material surface, and do not react with ternary material.Because the addition of carbon dioxide not only can play catalysis on ternary material surface
Effect, can also suppress the lithium nickelate in ternary material during carbon coating to reduce it is achieved that carbon-coating is on ternary material surface
Cladding, and be passed through carbon dioxide and can play catalytic action on ternary material surface, promote the formation of carbon-coating.
The cobalt nickel lithium manganate ternary material of the carbon coated of present invention preparation, is effectively reduced the mixed of lithium layer cationic
Row, improves first charge-discharge efficiency, improves lithium ion diffusion coefficient and the electronic conductivity of material；And reduce organic bath with
There is strong side reaction in electrode material, reduce impedance in charge and discharge process for the battery, improve the electrochemistry of NCM material
Energy.The preparation method that the present invention provides, equipment is relatively easy, and operation is few, and carbon structure is controlled, and the coated modified carbon prepared
Cobalt nickel lithium manganate ternary material, has higher battery capacity, cycle performance and high rate performance.Test result indicate that, the present invention
The lithium battery 1C capacity of the cobalt nickel lithium manganate ternary material preparation of the coated modified carbon of preparation is 33.6, after circulating 50 times, capacity
It still is able to reach 96.2%.
In order to further illustrate the present invention, a kind of nickle cobalt lithium manganate ternary material to present invention offer with reference to embodiments
The method of modifying of material is described in detail but it is to be understood that these embodiments are under premised on technical solution of the present invention
Implemented, given detailed embodiment and specific operating process, simply for further illustrate the present invention feature and
Advantage, rather than limiting to the claimed invention, protection scope of the present invention is also not necessarily limited to following embodiments.
Embodiment 1
The ternary material weighing 5g is placed in the middle part of the quartz ampoule that quartz boat is then put in quartz boat 5 horizontal positioned,
Again quartz ampoule is sent into the high-temperature region of heating furnace.
Open the air valve of the argon gas cylinder at 1, adjustment throughput is 50mL/min, ventilate 30min, to drain quartz ampoule 6
Interior air.It is then shut off the air valve of the argon gas cylinder at 1, open the carbon dioxide (CO at 22) methane at gas cylinder and 3
(CH4) gas cylinder air valve, throughput is all adjusted to 50mL/min, is passed through carbon dioxide and methane toward in quartz ampoule simultaneously.
Open heating furnace 4, setting programming rate is 20 DEG C/min, and quartz ampoule is risen to 1000 DEG C from room temperature, and 1000
DEG C keep 15min, allow methane cracking, generate carbon layer deposition on the surface of ternary material.
After question response terminates, stop heating to quartz ampoule, close the air valve of methane gas cylinder at dioxide bottle and 3 at 2,
Open the air valve of the argon gas cylinder at 1, treat that quartz ampoule and the sample of the inside cool to room temperature with the furnace under the protection of argon, take out
Quartz boat, obtains the cobalt nickel lithium manganate ternary material of required coated modified carbon.
The modified cobalt nickel lithium manganate ternary material that the embodiment of the present invention 1 obtains is measured, using weightening finish method, claims to produce
Thing 5.17g, finally obtaining carbon coating amount is 3.4%.
Referring to Fig. 1, Fig. 1 prepares the device flow process letter of carbon coating cobalt nickel lithium manganate ternary material for vapour deposition process of the present invention
Figure.Wherein 1 is the air valve of argon gas cylinder, and 2 is the air valve of dioxide bottle, and 3 is the air valve of methane gas cylinder, and 4 is heating furnace, 5
For quartz boat, 6 is quartz ampoule.
The modified cobalt nickel lithium manganate ternary material that the embodiment of the present invention 1 obtains is prepared into button cell and conventional nickel cobalt manganese
Sour lithium ternary material carries out electrical property measurement, does parallel contrast test, and result is prepared for the embodiment of the present invention referring to table 1, table 1
Modified cobalt nickel lithium manganate ternary material and conventional cobalt nickel lithium manganate ternary material performance comparison data.
Embodiment 2
The ternary material weighing 5g is placed in the middle part of the quartz ampoule that quartz boat is then put in quartz boat 5 horizontal positioned,
Again quartz ampoule is sent into the high-temperature region of heating furnace.
Open the air valve of the argon gas cylinder at 1, adjustment throughput is 50mL/min, ventilate 30min, to drain quartz ampoule 6
Interior air.It is then shut off the air valve of the argon gas cylinder at 1, open the air valve of methane gas cylinder at dioxide bottle and 3 at 2,
Throughput is adjusted to 50mL/min and 80mL/min respectively, is passed through carbon dioxide and methane toward in quartz ampoule simultaneously.
Open heating furnace 4, setting programming rate is 25 DEG C/min, and quartz ampoule is risen to 1100 DEG C from room temperature, and 1100
DEG C keep 20min, allow methane cracking, generate carbon layer deposition on the surface of ternary material.
After question response terminates, stop heating to quartz ampoule, close the air valve of methane gas cylinder at dioxide bottle and 3 at 2,
Open the air valve of the argon gas cylinder at 1, treat that quartz ampoule and the sample of the inside cool to room temperature with the furnace under the protection of argon, take out
Quartz boat, obtains the cobalt nickel lithium manganate ternary material of required coated modified carbon.
The modified cobalt nickel lithium manganate ternary material that the embodiment of the present invention 1 obtains is measured, using weightening finish method, claims to produce
Thing 5.43g, finally obtaining carbon coating amount is 8.6%.
The modified cobalt nickel lithium manganate ternary material that the embodiment of the present invention 1 obtains is prepared into button cell and conventional nickel cobalt manganese
Sour lithium ternary material carries out electrical property measurement, does parallel contrast test, and result is prepared for the embodiment of the present invention referring to table 1, table 1
Modified cobalt nickel lithium manganate ternary material and conventional cobalt nickel lithium manganate ternary material performance comparison data.
Embodiment 3
The ternary material weighing 10g is placed in the quartz ampoule that quartz boat is then put in quartz boat 5 horizontal positioned
Portion, then quartz ampoule is sent into the high-temperature region of heating furnace.
Open the air valve of the argon gas cylinder at 1, adjustment throughput is 50mL/min, ventilate 40min, to drain quartz ampoule 6
Interior air.It is then shut off the air valve of the argon gas cylinder at 1, open the air valve of methane gas cylinder at dioxide bottle and 3 at 2,
Throughput is adjusted to 60mL/min and 80mL/min respectively, is passed through carbon dioxide and methane toward in quartz ampoule simultaneously.
Open heating furnace, setting programming rate is 25 DEG C/min, and quartz ampoule is risen to 1100 DEG C from room temperature, and 1100
DEG C keep 20min, allow methane cracking, generate carbon layer deposition on the surface of ternary material.
After question response terminates, stop heating to quartz ampoule, close the air valve of methane gas cylinder at dioxide bottle and 3 at 2,
Open the air valve of the argon gas cylinder at 1, treat that quartz ampoule and the sample of the inside cool to room temperature with the furnace under the protection of argon, take out
Quartz boat, obtains the cobalt nickel lithium manganate ternary material of required coated modified carbon.
The modified cobalt nickel lithium manganate ternary material that the embodiment of the present invention 1 obtains is measured, using weightening finish method, claims to produce
Thing 10.64g, finally obtaining carbon coating amount is 6.4%.
The modified cobalt nickel lithium manganate ternary material that the embodiment of the present invention 1 obtains is prepared into button cell and conventional nickel cobalt manganese
Sour lithium ternary material carries out electrical property measurement, does parallel contrast test,
Method of testing：It is assembled into the button cell of 2016 models.Anode formula is：Mass ratio 96% active material, 2%
Conductive agent SP (SP-Li, TIMICAL), 2% bonding agent polyvinylidene fluoride (PVDF900, ARKEMA).Slurry uniformly coats
Thickness be 16 microns aluminium foil on, surface density be 0.164g/cm2, a diameter of 13mm of disk.Negative pole be lithium piece (diameter 14mm,
Thick 0.6mm), barrier film is 16 microns of thick Celgard2320 barrier films, and electrolyte is LiPF containing 1mol/L6With 5% mass ratio
(volume ratio is 3 to the ethylene carbonate-diethyl carbonate-Allyl carbonate of vinylene carbonate:3:1) mixed solution.For contrasting,
Assemble using normal conventional NCM ternary material is 2016 model button cells of positive pole simultaneously.Afterwards 0.2C is carried out to battery
Capacity (1C=35mA), multiplying power (1C) and cycle performance (0.2C charge and discharge cycles) are tested.
Test result referring to table 1, modified cobalt nickel lithium manganate ternary material and conventional nickel that table 1 is prepared for the embodiment of the present invention
Cobalt manganic acid lithium ternary material performance comparison data.
The modified cobalt nickel lithium manganate ternary material of table 1 embodiment of the present invention preparation and conventional cobalt nickel lithium manganate ternary material
Can correction data
As shown in Table 1, after NCM ternary material carbon coated, high rate performance and cycle performance are lifted.Additionally, with carbon coating
The lifting of amount, capacity is slightly decreased, but high rate performance and cycle performance have been lifted.
Above a kind of coated modified carbon method of cobalt nickel lithium manganate ternary material that the present invention provides is carried out detailed
Introduce, specific case used herein is set forth to the principle of the present invention and embodiment, the explanation of above example
It is only intended to help and understands the method for the present invention and its core concept, including best mode, and also make any of this area
Technical staff can put into practice the present invention, including manufacture with using any device or system, and the method implementing any combination.Should
When pointing out, for those skilled in the art, under the premise without departing from the principles of the invention, can also be to this
Invention carries out some improvement and modifies, and these improve and modify and also fall in the protection domain of the claims in the present invention.The present invention
The scope of patent protection is defined by the claims, and may include those skilled in the art it is conceivable that other embodiment.
If these other embodiments have the structural element being not different from claim character express, or if they include with
The equivalent structural elements of the character express of claim no essence difference, then these other embodiments also should be included in right will
In the range of asking.
Claims (10)
1. a kind of method of modifying of cobalt nickel lithium manganate ternary material is it is characterised in that comprise the following steps：
A) under conditions of carbon-source gas and protective gas, by nickel-cobalt lithium manganate material after vapour deposition, obtain carbon bag
The modified nickel-cobalt lithium manganate material covering.
2. method of modifying according to claim 1 is it is characterised in that described carbon source is included in alkane, alkene and alkynes
One or more.
3. method of modifying according to claim 1 is it is characterised in that described carbon source includes methane, ethane, ethylene, propylene
One or more of with acetylene；
Described protective gas includes one or more of carbon dioxide, nitrogen and noble gases.
4. method of modifying according to claim 1 it is characterised in that described carbon-source gas be passed through speed be 20～
100mL/min.
5. method of modifying according to claim 1 it is characterised in that described protective gas be passed through speed be 30～
150mL/min.
6. the method for modifying according to Claims 1 to 5 any one is it is characterised in that the temperature of described vapour deposition is
500～1500 DEG C；
The time of described vapour deposition is 5～120min；
The heating rate of the heating process of described vapour deposition is 5～30 DEG C/min.
7. method of modifying according to claim 1 is it is characterised in that the modified nickel-cobalt lithium manganate material of described carbon coating
Carbon coating amount is 3%～10%.
8. method of modifying according to claim 1, it is characterised in that also including before described vapour deposition, is passed through gas
The step of exclusion air；
Described gas includes nitrogen and/or noble gases；
The speed that is passed through of described gas is 20～100mL/min；
The time that is passed through of described gas is 10～120min.
9. the method for modifying according to claim 7～9 any one is it is characterised in that described nickel-cobalt lithium manganate material is
Nickelic tertiary cathode material；
Shown in the chemical formula such as formula (II) of described nickelic tertiary cathode material,
LiNi1-x-yCoxMnyO2(II)；
Wherein, (1-x-y) >=0.5, x ＞ 0, y ＞ 0.
10. a kind of lithium ion battery is it is characterised in that described positive pole includes the modification prepared by claim 1～9 any one
Nickel-cobalt lithium manganate material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610978496.9A CN106450217B (en) | 2016-11-07 | 2016-11-07 | Method for modifying nickel cobalt lithium manganate ternary material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610978496.9A CN106450217B (en) | 2016-11-07 | 2016-11-07 | Method for modifying nickel cobalt lithium manganate ternary material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106450217A true CN106450217A (en) | 2017-02-22 |
| CN106450217B CN106450217B (en) | 2020-08-04 |
Family
ID=58207521
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610978496.9A Active CN106450217B (en) | 2016-11-07 | 2016-11-07 | Method for modifying nickel cobalt lithium manganate ternary material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106450217B (en) |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107068972A (en) * | 2017-03-22 | 2017-08-18 | 江苏元景锂粉工业有限公司 | The ternary material anode pole piece and its lithium ion battery of a kind of quick charge |
| CN108258226A (en) * | 2018-01-25 | 2018-07-06 | 深圳市德方纳米科技股份有限公司 | A kind of carbon coating tertiary cathode material and preparation method thereof |
| CN108493406A (en) * | 2018-02-28 | 2018-09-04 | 中航锂电（洛阳）有限公司 | Nickelic tertiary cathode material is as application of the catalyst in terms of preparing carbon nanotube, positive electrode and preparation method thereof, lithium battery |
| CN108550810A (en) * | 2018-04-12 | 2018-09-18 | 合肥国轩高科动力能源有限公司 | Preparation method of cerium-doped and carbon-coated modified ternary positive electrode material |
| CN108598448A (en) * | 2018-06-27 | 2018-09-28 | 合肥工业大学 | A kind of three-dimensional structure carbon coating cobalt acid manganese nano-material and preparation method and application |
| CN108963239A (en) * | 2018-08-14 | 2018-12-07 | 上海力信能源科技有限责任公司 | Nickel-cobalt lithium manganate cathode material of coated by titanium dioxide and preparation method thereof |
| CN109167053A (en) * | 2018-07-03 | 2019-01-08 | 江苏乐能电池股份有限公司 | A kind of preparation method of high density trielement composite material |
| CN110137483A (en) * | 2019-06-18 | 2019-08-16 | 贵州梅岭电源有限公司 | A kind of nickle cobalt lithium manganate composite material and preparation method and application |
| CN113044893A (en) * | 2021-03-12 | 2021-06-29 | 电子科技大学 | Method for carrying out carbon coating modification on high-nickel ternary material |
| CN113346081A (en) * | 2021-05-27 | 2021-09-03 | 南京市永信合智能科技有限公司 | Method for preparing carbon-coated ternary cathode nano material by alkyne oxidation |
| CN114988492A (en) * | 2022-05-31 | 2022-09-02 | 西安合升汇力新材料有限公司 | Nickel-rich ternary cathode material and preparation method and application thereof |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005158721A (en) * | 2003-10-31 | 2005-06-16 | Hitachi Maxell Ltd | Electrode material of nonaqueous secondary battery, its process of manufacture, and nonaqueous secondary battery using electrode material |
| CN101000960A (en) * | 2006-12-29 | 2007-07-18 | 深圳市贝特瑞电子材料有限公司 | Composite lithium titanate electrode material and preparation method thereof |
| CN101217195A (en) * | 2007-12-28 | 2008-07-09 | 龚思源 | A lithium ion battery anode material of lithium iron phosphate and the corresponding vapor deposition and cladding method of conductive network |
| CN101333650A (en) * | 2007-06-27 | 2008-12-31 | 中国科学院金属研究所 | Method for uniformly and controllably coating conducting carbon layer at surface of LiFePO4 granule surface |
| CN101527353A (en) * | 2009-03-10 | 2009-09-09 | 重庆大学 | Lithium ion battery anode composite material and manufacturing method thereof |
| CN101853931A (en) * | 2009-04-01 | 2010-10-06 | 中国科学院金属研究所 | Preparation method of porous conductive LiFePO4 positive plate used in lithium ion battery |
| CN102303860A (en) * | 2011-09-30 | 2012-01-04 | 中南大学 | Method for synthesizing lithium iron phosphate by ultrasonic spray solid-phase sintering |
| CN102723465A (en) * | 2011-06-15 | 2012-10-10 | 中国科学院金属研究所 | Preparation method of porous LiFePO4 bulk electrode for lithium ion batteries |
| CN103887510A (en) * | 2014-03-27 | 2014-06-25 | 电子科技大学 | Preparation method of carbon-coated lithium ferrous silicate compound positive electrode material |
| CN104795554A (en) * | 2015-05-05 | 2015-07-22 | 天津巴莫科技股份有限公司 | Method for inhibiting spinel lithium titanate from generating gas |
-
2016
- 2016-11-07 CN CN201610978496.9A patent/CN106450217B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005158721A (en) * | 2003-10-31 | 2005-06-16 | Hitachi Maxell Ltd | Electrode material of nonaqueous secondary battery, its process of manufacture, and nonaqueous secondary battery using electrode material |
| CN101000960A (en) * | 2006-12-29 | 2007-07-18 | 深圳市贝特瑞电子材料有限公司 | Composite lithium titanate electrode material and preparation method thereof |
| CN101333650A (en) * | 2007-06-27 | 2008-12-31 | 中国科学院金属研究所 | Method for uniformly and controllably coating conducting carbon layer at surface of LiFePO4 granule surface |
| CN101217195A (en) * | 2007-12-28 | 2008-07-09 | 龚思源 | A lithium ion battery anode material of lithium iron phosphate and the corresponding vapor deposition and cladding method of conductive network |
| CN101527353A (en) * | 2009-03-10 | 2009-09-09 | 重庆大学 | Lithium ion battery anode composite material and manufacturing method thereof |
| CN101853931A (en) * | 2009-04-01 | 2010-10-06 | 中国科学院金属研究所 | Preparation method of porous conductive LiFePO4 positive plate used in lithium ion battery |
| CN102723465A (en) * | 2011-06-15 | 2012-10-10 | 中国科学院金属研究所 | Preparation method of porous LiFePO4 bulk electrode for lithium ion batteries |
| CN102303860A (en) * | 2011-09-30 | 2012-01-04 | 中南大学 | Method for synthesizing lithium iron phosphate by ultrasonic spray solid-phase sintering |
| CN103887510A (en) * | 2014-03-27 | 2014-06-25 | 电子科技大学 | Preparation method of carbon-coated lithium ferrous silicate compound positive electrode material |
| CN104795554A (en) * | 2015-05-05 | 2015-07-22 | 天津巴莫科技股份有限公司 | Method for inhibiting spinel lithium titanate from generating gas |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107068972A (en) * | 2017-03-22 | 2017-08-18 | 江苏元景锂粉工业有限公司 | The ternary material anode pole piece and its lithium ion battery of a kind of quick charge |
| CN108258226A (en) * | 2018-01-25 | 2018-07-06 | 深圳市德方纳米科技股份有限公司 | A kind of carbon coating tertiary cathode material and preparation method thereof |
| CN108493406B (en) * | 2018-02-28 | 2020-09-15 | 中航锂电（洛阳）有限公司 | Application of high-nickel ternary cathode material as catalyst in preparation of carbon nanotube, cathode material and preparation method thereof, and lithium battery |
| CN108493406A (en) * | 2018-02-28 | 2018-09-04 | 中航锂电（洛阳）有限公司 | Nickelic tertiary cathode material is as application of the catalyst in terms of preparing carbon nanotube, positive electrode and preparation method thereof, lithium battery |
| CN108550810A (en) * | 2018-04-12 | 2018-09-18 | 合肥国轩高科动力能源有限公司 | Preparation method of cerium-doped and carbon-coated modified ternary positive electrode material |
| CN108598448A (en) * | 2018-06-27 | 2018-09-28 | 合肥工业大学 | A kind of three-dimensional structure carbon coating cobalt acid manganese nano-material and preparation method and application |
| CN109167053A (en) * | 2018-07-03 | 2019-01-08 | 江苏乐能电池股份有限公司 | A kind of preparation method of high density trielement composite material |
| CN108963239A (en) * | 2018-08-14 | 2018-12-07 | 上海力信能源科技有限责任公司 | Nickel-cobalt lithium manganate cathode material of coated by titanium dioxide and preparation method thereof |
| CN108963239B (en) * | 2018-08-14 | 2020-06-30 | 上海力信能源科技有限责任公司 | Preparation method of titanium dioxide coated nickel cobalt lithium manganate positive electrode material |
| CN110137483A (en) * | 2019-06-18 | 2019-08-16 | 贵州梅岭电源有限公司 | A kind of nickle cobalt lithium manganate composite material and preparation method and application |
| CN110137483B (en) * | 2019-06-18 | 2022-03-22 | 贵州梅岭电源有限公司 | Nickel cobalt lithium manganate composite material and preparation method and application thereof |
| CN113044893A (en) * | 2021-03-12 | 2021-06-29 | 电子科技大学 | Method for carrying out carbon coating modification on high-nickel ternary material |
| CN113346081A (en) * | 2021-05-27 | 2021-09-03 | 南京市永信合智能科技有限公司 | Method for preparing carbon-coated ternary cathode nano material by alkyne oxidation |
| CN114988492A (en) * | 2022-05-31 | 2022-09-02 | 西安合升汇力新材料有限公司 | Nickel-rich ternary cathode material and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106450217B (en) | 2020-08-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106450217A (en) | Method for modifying nickel cobalt lithium manganate ternary material | |
| Wei et al. | Lithium-rich manganese-based cathode materials with highly stable lattice and surface enabled by perovskite-type phase-compatible layer | |
| Zhang et al. | Surface-coated LiNi0. 8Co0. 1Mn0. 1O2 (NCM811) cathode materials by Al2O3, ZrO2, and Li2O-2B2O3 thin-layers for improving the performance of lithium ion batteries | |
| Zhai et al. | Improving the cycling and air-storage stability of LiNi 0.8 Co 0.1 Mn 0.1 O 2 through integrated surface/interface/doping engineering | |
| Zhang et al. | High-voltage LiCoO2 cathodes for high-energy-density lithium-ion battery | |
| CN112670506B (en) | Nickel-cobalt-manganese-tantalum composite quaternary positive electrode material coated by fast ion conductor and preparation method thereof | |
| CN108172799A (en) | A kind of tertiary cathode material of nucleocapsid structure lithium ion battery and preparation method thereof | |
| CN107910529A (en) | A kind of ternary cathode material of lithium ion battery of manganese Base Metal organic frame compound cladding and preparation method thereof | |
| CN108390039A (en) | A kind of nickelic anode material of lithium battery that double oxide coats altogether and preparation method | |
| CN109786687A (en) | A kind of preparation method to sacrifice template induced synthesis metal oxide cladding nickel-cobalt-manganese ternary anode material for lithium-ion batteries | |
| CN107834050A (en) | A kind of lithium-enriched cathodic material of lithium ion battery and its improved method | |
| CN107394156A (en) | A kind of method of modifying and its modified anode material of the lithium-rich manganese-based anode material for lithium-ion batteries based on organic matter ammoniacal liquor | |
| Hu et al. | Enhanced high-temperature performance and thermal stability of lithium-rich cathode via combining full concentration gradient design with surface spinel modification | |
| CN102593508B (en) | Lithium ion battery | |
| Zhang et al. | High-rate layered lithium-rich cathode nanomaterials for lithium-ion batteries synthesized with the assist of carbon spheres templates | |
| CN108630923A (en) | Nickel cobalt lithium aluminate cathode material, preparation method and the lithium battery of gradient sodium ion doping | |
| Hsieh et al. | Roll-to-roll atomic layer deposition of titania nanocoating on thermally stabilizing lithium nickel cobalt manganese oxide cathodes for lithium ion batteries | |
| CN106299295A (en) | A kind of porous micro-nano structure lithium-enriched cathodic material of lithium ion battery with fusiformis pattern and preparation method thereof | |
| CN109713260A (en) | A kind of method of modifying of Phosphate coating lithium-rich manganese-based anode material | |
| TWI667837B (en) | A lithium-rich oxide positive electrode material and the preparation method thereof and a lithium-ion battery | |
| Xin et al. | Conformal spinel/layered heterostructures of Co3O4 shells grown on single-crystal Li-rich nanoplates for high-performance lithium-ion batteries | |
| Li et al. | Heterostructured lithium-rich layered oxides core@ spinel-MgAl2O4 shell as high-performance cathode for lithium-ion batteries | |
| Meng et al. | Improving cycling stability and suppressing voltage fade of layered lithium-rich cathode materials via SiO 2 shell coating | |
| WO2018068702A1 (en) | Positive electrode tab and lithium-ion battery having electrode tab | |
| Jiao et al. | Surface modification single crystal Li-rich Li1. 2Mn0. 54Ni0. 13Co0. 13O2 as high performance cathode materials for Li-ion batteries |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |