CN107275606A - A kind of carbon coating spinel lithium manganate nano composite material and preparation method and application - Google Patents
A kind of carbon coating spinel lithium manganate nano composite material and preparation method and application Download PDFInfo
- Publication number
- CN107275606A CN107275606A CN201710442178.5A CN201710442178A CN107275606A CN 107275606 A CN107275606 A CN 107275606A CN 201710442178 A CN201710442178 A CN 201710442178A CN 107275606 A CN107275606 A CN 107275606A
- Authority
- CN
- China
- Prior art keywords
- lithium manganate
- carbon
- nano
- carbon coating
- spinel lithium
- 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
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 title claims abstract description 56
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 239000000463 material Substances 0.000 title claims abstract description 48
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 46
- 238000000576 coating method Methods 0.000 title claims abstract description 41
- 239000011248 coating agent Substances 0.000 title claims abstract description 39
- 229910052596 spinel Inorganic materials 0.000 title claims abstract description 33
- 239000011029 spinel Substances 0.000 title claims abstract description 33
- 239000002114 nanocomposite Substances 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 33
- 239000002131 composite material Substances 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 21
- 239000003990 capacitor Substances 0.000 claims abstract description 12
- 239000011149 active material Substances 0.000 claims abstract description 11
- 150000002500 ions Chemical class 0.000 claims abstract description 8
- 238000000498 ball milling Methods 0.000 claims description 53
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 claims description 47
- 239000002245 particle Substances 0.000 claims description 9
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- 229910052744 lithium Inorganic materials 0.000 claims description 8
- 239000011230 binding agent Substances 0.000 claims description 5
- 238000000227 grinding Methods 0.000 claims description 5
- 229910021389 graphene Inorganic materials 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 3
- LLYXJBROWQDVMI-UHFFFAOYSA-N 2-chloro-4-nitrotoluene Chemical compound CC1=CC=C([N+]([O-])=O)C=C1Cl LLYXJBROWQDVMI-UHFFFAOYSA-N 0.000 claims description 2
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 2
- 239000004917 carbon fiber Substances 0.000 claims description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 14
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 14
- 239000003792 electrolyte Substances 0.000 abstract description 6
- 239000002105 nanoparticle Substances 0.000 abstract description 6
- 238000005516 engineering process Methods 0.000 abstract description 5
- 230000005540 biological transmission Effects 0.000 abstract description 4
- 230000008569 process Effects 0.000 abstract description 4
- 238000009792 diffusion process Methods 0.000 abstract description 3
- 239000006258 conductive agent Substances 0.000 abstract description 2
- 238000000713 high-energy ball milling Methods 0.000 abstract 1
- 238000005457 optimization Methods 0.000 abstract 1
- 238000005253 cladding Methods 0.000 description 15
- 239000000843 powder Substances 0.000 description 8
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 125000004430 oxygen atom Chemical group O* 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 239000008103 glucose Substances 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- MMIPFLVOWGHZQD-UHFFFAOYSA-N manganese(3+) Chemical compound [Mn+3] MMIPFLVOWGHZQD-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000004570 mortar (masonry) Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 1
- 229910015645 LiMn Inorganic materials 0.000 description 1
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000005030 aluminium foil Substances 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- -1 graphite Alkene Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000037427 ion transport Effects 0.000 description 1
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 description 1
- LBSANEJBGMCTBH-UHFFFAOYSA-N manganate Chemical compound [O-][Mn]([O-])(=O)=O LBSANEJBGMCTBH-UHFFFAOYSA-N 0.000 description 1
- 229910001437 manganese ion Inorganic materials 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000005381 potential energy Methods 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical compound FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 238000001238 wet grinding Methods 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/46—Metal oxides
-
- 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
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- 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
-
- 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
-
- 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
- Y02E60/13—Energy storage using capacitors
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Electrochemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Power Engineering (AREA)
- Materials Engineering (AREA)
- Composite Materials (AREA)
- Nanotechnology (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Abstract
The invention discloses a kind of carbon coating spinel lithium manganate nano composite material and preparation method thereof, by high-energy ball milling one-step method, micron order spinel lithium manganate is ground into nanoscale while making carbon material be uniformly wrapped on nano grain surface.The application of nano particle, shortens ion diffusion and transmission path of the material in charge and discharge process；Carbon coating also can avoid lithium manganate cathode from directly being contacted with electrolyte, can greatly improve the high rate performance and cycle performance of lithium ion battery and hybrid super capacitor while active material electric conductivity is improved；Because clad has been constituted in conductive network, subsequent applications without extra addition conductive agent again.Compared with traditional preparation methods, present invention greatly simplifies the preparation technology of composite, one-step method prepares the carbon coating spinel lithium manganate nano composite material of performance optimization.
Description
Technical field
The present invention relates to field of compound material, more particularly to a kind of LiMn2O4 carbon nano-composite material and its preparation are with answering
With.
Background technology
Into 21 century, the mankind are faced with the severe challenge of energy crisis and environmental problem, tap a new source of energy (solar energy,
Wind energy, biological energy source, tide energy, nuclear energy, underground heat) and regenerative resource be to solve environmental pollution and realize the important of sustainable development
Behave.As a kind of important electronic device, energy storage device plays critically important role.Wherein, lithium ion battery, super
Level capacitor and the hybrid super capacitor being combined into by both turn into most potential energy storage device.
Spinel lithium manganate LiMn2O4ABUNDANT NATUREAL RESOURSES, it is cheap, it is safe, easily prepare and nontoxic, it has also become
Most potential anode material for lithium-ion batteries, and by widely commercial applications.Spinelle LiMn2O4Belong to cubic system, space
Group is Fd3m, oxygen atom formation face-centered cubic closs packing, the 32e positions for the point group that takes up space；Manganese ion is located at octahedron 16d,
Octahedra 16c vacant；Lithium ion is then located at 8a, tetrahedron, 8a and the 16c three-dimensional channels for forming lithium ion diffusion, helps
Occur rapidly to take off in lattice in lithium ion/embedding.LiMn2O4 compares other types positive electrode with higher high rate performance,
But the need for still can not meeting the application of energy storage field；And in charge and discharge process material granule surface Mn3+Dissolving cause point
Spinel structure defect is produced so that capacity attenuation is rapid, cycle life shortens.For this problem, ion doping, active material are received
The methods such as meter Hua, Surface coating high conductivity material are widely studied and applied.
Jiang Qian is pretty et al. to have invented a kind of agraphitic carbon cladding LiMn2O4 composite.First pass through hydro-thermal method synthetic lithium manganate
Powder, is placed in tube furnace after then the powder is uniformly mixed with glucose, and 800 degrees Celsius of sintering 2 are protected in argon gas atmosphere
Hour, obtain agraphitic carbon cladding LiMn2O4 composite.But product grain is thick made from this method, in charge and discharge process
Ion diffusion path is longer, ion deinsertion is obstructed, and is not suitable for carrying out high power charging-discharging, it is impossible to meet electronic device for quick
The requirement of discharge and recharge.And hydro-thermal method and high temperature cabonization are difficult to commercialization due to reasons such as its low production efficiency, condition harshnesses.
Li Xinhai et al. is by magnetically controlled sputter method by graphite coat in mangaic acid lithium electrode surface.Conventional electricity is being made in the method
One layer of graphite is extremely sputtered on the mangaic acid lithium electrode prepared by magnetron sputtering afterwards, so that graphite coat LiMn2O4 electricity is made
Pole.Carbon coating layer is only coated on one layer of most surface in this method, and each lithium manganate particle is not coated uniformly, it is impossible to
Conductive network is formed between active material particle so that electric conductivity does not improve a lot；And it is commercialized micron-sized mangaic acid
Lithium is not crushed, and still particle is thick for active material, is not conducive to Stability Analysis of Structures in the progress and cyclic process of fast charging and discharging
The holding of property.
Liu Jian floods et al. have invented species graphene coated adulterated lithium manganate composite positive pole and preparation method thereof (specially
Profit number：The A of CN 105655576), by ball milling manganese dioxide and lithium carbonate, mangaic acid powder for lithium is prepared through solid phase reaction, so
Class graphene presoma is added in mangaic acid powder for lithium afterwards and is well mixed, high-temperature calcination obtains graphene/LiMn2O4 composite powder
Body, is finally thermally treated resulting in graphene coated adulterated lithium manganate composite positive pole in atmosphere.It is compound that the method is prepared
Material graphene coated is insufficient, and step of preparation process is various, and is directed to high-temperature heat treatment, uneconomical environmental protection.
Liu Taotao et al. has invented a kind of preparation method (CN 102916178 of coated modified carbon manganate cathode material for lithium
A), LiMn2O4 and organic carbon source and carbided catalyst are configured to mixed solution, by after spray dryer mist projection granulating to powder
End obtains the composite in 300 DEG C of -450 DEG C of sintering 0.5h-4h, so as to obtain the composite.Effectively increase electricity
Pole electric conductivity simultaneously avoids electrode and directly contacted with electrolyte, but the method does not carry out dispersion and fining to lithium manganate particle,
Cause gained composite particles thick, have a strong impact on the high rate performance of electrode material.
Liao Wen person of outstanding talent et al. has invented a kind of preparation method (patent No. for coating LiMn2O4：The A of CN 103996840), by gold
Category oxide is coated on LiMn2O4 surface.LiMn2O4 and the metal oxide prepared are added to the water scattered stir by the method
To suspension, product centrifuge washing is dried and calcined afterwards obtain metal oxide cladding LiMn2O4.The electrode that the method is obtained
Material has more preferable high temperature cyclic performance, but electrode material electric conductivity is still very poor, it is impossible to improve the high rate performance of battery.
Tao Haisheng et al. has invented a kind of core shell structure LiMn2O4 and preparation method thereof (A of CN 104282902), uses carbon
Sour manganese and lithium carbonate are that spinel lithium manganate is made by high temperature solid state reaction in raw material, using deionized water by LiMn2O4 and oxalic acid
After the well mixed drying of cobalt, the LiMn2O4 for being coated with cobalt oxide core shell structure is made by heat treatment.The electricity that the method is prepared
Pole material technology is complicated, and cladding is incomplete, and electric conductivity is poor, and high rate performance owes excellent.
The poplar winter is fine et al. to have invented a kind of coating modification LiMn2O4 and preparation method thereof (patent No.：CN 105655576
A), LiMn2O4 is uniformly first mixed into acquisition presoma with boron source with the lithium source needed for preparing lithium tetraborate, then before high-temperature calcination
Drive body and obtain lithium tetraborate cladding LiMn2O4 composite.The material granule that the method is prepared is thick, and electric conductivity is poor, causes
Lithium ion battery high rate performance is not good.
Zhang Jianfeng on《LiMn2O4The coated modified carbon and Electrochemical Properties of electrode material》Mixed certainly using melting
Method prepares LiMn2O4Powder, and be carbon source with glucose, it is prepared for the LiMn of carbon coated2O4Material.But its carbon coating method is grasped
Make complicated condition, time-consuming, controllability is poor, influence factor is more, different batches are difficult to reach stable performance, economic benefit
It is bad, it is difficult in mass production application in recent years.
Existing carbon coating spinel lithium manganate is general to carry out carbon coating needs at high temperature by being pyrolyzed organic compound
(~600 degrees Celsius) progress, and LiMn2O4 easily causes the missing of oxygen atom and causes hydraulic performance decline at high temperature.Pass through chemistry
Vapour deposition process (CVD) cladding carbon material can equally cause the loss of oxygen atom.Being badly in need of one kind at present can be carried out at low temperature
Method for coating.
The content of the invention
In order to overcome above-mentioned deficiency, the invention provides a kind of simple and effective one-step synthesis method carbon-coated nano LiMn2O4
And preparation method and application, LiMn2O4 nanosizing is combined with carbon coating technology, substantially increase LiMn2O4 specific capacity, times
The chemical properties such as rate performance, cycle life.Herein described method for synthesizing composite material is simple, high rate performance good, in lithium
Ion battery, hybrid super capacitor field have broad application prospects.Carbon coating manganese can be prepared on a large scale at normal temperatures
Sour lithium nano composite material, the one-step method for realizing nano composite material is prepared on a large scale.
To achieve these goals, the present invention is adopted the following technical scheme that：
Application of the nano-scale carbon material in ball-milling method prepares carbon coating spinel lithium manganate nano composite material.
Present invention also offers a kind of carbon coating spinel lithium manganate nano composite material, the composite by weighing as follows
Measure the raw material composition of number：1-3 parts of micron order LiMn2O4s, 1 part of nano-scale carbon material, the LiMn2O4 are uniformly coated with carbon material
Together.
In order to realize that LiMn2O4 nanosizing is combined with carbon coating technology, while the oxygen loss of LiMn2O4 at high temperature is avoided,
Structure change rule of the present invention to LiMn2O4 in nanosizing and carbon coating process has carried out system research, after many experiments are groped
It was found that：By micron order LiMn2O4 and nano grade inorganic carbon material mixing and ball milling, the specific capacity, forthright again of LiMn2O4 can be effectively improved
The chemical properties such as energy, cycle life, and because ball milling can be carried out at room temperature, the generation of oxygen defect will not be caused.
Previous experiments of the present invention show：A certain amount of manganese element can be caused to be lost in the independent ball milling of business LiMn2O4, caused
Hydraulic performance decline.And use nano grade inorganic carbon material with micron order LiMn2O4 1：, can be effective under 1-3 ratio during mixing and ball milling
Prevent the loss of manganese element.Therefore, currently preferred nano grade inorganic carbon material and micron order LiMn2O4 mixed proportion are 1：
1-3。
It is preferred that, the particle diameter of the composite is 20nm~2000nm.
It is preferred that, the LiMn2O4 includes spherical, octahedral build business spinel lithium manganate one or more；
It is preferred that, the carbon material be conductive black, graphene, CNT, carbon fiber, electrically conductive ink in one kind or
It is a variety of.
Present invention also offers a kind of preparation method of carbon coating spinel lithium manganate nano composite material, including：
By micron order LiMn2O4, nano-scale carbon material be well mixed, ball milling, carbon coating spinel lithium manganate nanometer is produced multiple
Condensation material.
The transmission of lithium ion and electronics can be effectively facilitated by the nanosizing of LiMn2O4 in the present invention：Small-size grains ratio
Surface area is bigger with surface area/volume ratio, it is ensured that active material is fully contacted with electrolyte, is filled active material
Divide and utilize, so as to improve active material specific capacity；And nanostructured shortens the transmission path of ion, it is beneficial to the fast of ion
Fast deintercalation, so as to substantially increase the high rate performance of material.Carbon material cladding is effectively improved leading between active material particle
Electrically.Clad can be effectively facilitated lithium ion transport, holding structure stability and the dissolving for alleviating Manganic ion.
It is preferred that, the condition of the ball milling is：Ratio of grinding media to material 9~10:1st ,-the 580r/min of rotating speed 200, time 2-24h；
Ball grinding method of the present invention is simple to operate, requires low to working condition, is carried out in air at room temperature, raw material sources
Extensively, can the stable high rate capability carbon coating spinel lithium manganate nano composite material of mass production performance.
It is preferred that, the ball milling is using nonmetallic ball grinder and nonmetallic ball milling pearl, preferably agate jar and agate
Ball milling pearl, wherein, the small ball's diameter 2-15mm, spherical tank volume 50-200ml；
It is preferred that, the ball milling uses high energy ball mill, preferably planetary ball mill.
Present invention also offers carbon coating spinel lithium manganate nano composite material prepared by any above-mentioned method.
Present invention also offers a kind of preparation method of carbon coating spinel lithium manganate nano composite material electrode, including：
By micron order LiMn2O4, nano-scale carbon material be well mixed, ball milling, carbon coating spinel lithium manganate is obtained nano combined
Material；
Using above-mentioned carbon coating spinel lithium manganate nano composite material as active material, and binding agent, solvent complex,
Obtain coating；
Above-mentioned coating is coated on basal electrode, produced.
Present invention also offers any above-mentioned carbon coating spinel lithium manganate nano composite material prepare electrode, lithium from
Applied in sub- battery, hybrid super capacitor.
Beneficial effects of the present invention
(1) LiMn2O4 that the present invention is used is commercialization LiMn2O4, and wide material sources, performance are stable.
(2) present invention utilizes ball-milling method, one-step synthesis carbon coating LiMn2O4 nano composite material, simple to operate, cost
It is low.
(3) the carbon coating LiMn2O4 nanoparticle size that the present invention is synthesized is small, shortens material in charge and discharge process
Ion spreads and transmission path, can greatly improve the high rate performance of lithium ion battery and hybrid super capacitor.
(4) present invention is remarkably improved manganate cathode material for lithium electric conductivity, and avoid by carbon coating lithium manganate particle
Lithium manganate cathode is directly contacted with electrolyte.
(5) carbon material is directly coated on surface of active material by the present invention, uniform conductive network is constituted, in follow-up energy storage
Without additionally adding conductive agent in device application.
(6) present invention is other carbon coating lithium-containing oxides composites, such as carbon-coated LiFePO 4 for lithium ion batteries, carbon coating lithium titanate
The new method of offer is synthesized etc. nano composite material.
(7) preparation method of the present invention is simple, detection efficiency is high, practical, it is easy to promote.
Brief description of the drawings
The Figure of description for constituting the part of the application is used for providing further understanding of the present application, and the application's shows
Meaning property embodiment and its illustrate be used for explain the application, do not constitute the improper restriction to the application.
The original business of Fig. 1 amplifies 20000 times of scanning electron microscope (SEM) photographs with spherical spinel LiMn2O4；
Fig. 2 business 20000 times of scanning electron microscope (SEM) photographs of amplification after LiMn2O4 ball milling；
Fig. 3 conductive black super P cladding LiMn2O4 nano particles amplify 50000 times of scanning electron microscope (SEM) photographs；
Fig. 4 conductive black super P cladding LiMn2O4 nano particles carbon, manganese, oxygen element distribution map；
Fig. 5 conductive black super P cladding LiMn2O4 nano particles are used as water system mixed capacitor positive pole cyclic voltammogram；
Fig. 6 conductive black super P cladding LiMn2O4 nano particles are used as water system mixed capacitor high rate performance figure.
Embodiment
It is noted that described further below is all exemplary, it is intended to provide further instruction to the application.Unless another
Indicate, all technologies used herein and scientific terminology are with usual with the application person of an ordinary skill in the technical field
The identical meanings of understanding.
A kind of carbon material cladding nanometer lithium manganate composite and preparation method and application, (1) material therefor is business
With LiMn2O4 and carbon material；(2) it is nanoscale lithium manganate particle to crush business micron order LiMn2O4；(3) carbon material is led to
Cross ball milling and be directly coated on nanometer lithium manganate particle surface.Carbon material is equably coated while dispersion and fining lithium manganate particle
In its particle surface, electrode material electric conductivity is improved.While lithium ion battery is lifted with mixed capacitor cycle performance, show
Write ground and improve its high rate performance.
Carbon material of the present invention coats the preparation method of nanometer lithium manganate, comprises the steps：
1) business LiMn2O4 and carbon material are taken, is placed in ball grinder；
2) matching somebody with somebody takes certain proportion ball milling pearl to be placed in above-mentioned ball grinder；
3) ball milling cover lid is sealed and is installed on ball mill and carry out ball milling
Described carbon material coats the preparation method of nanometer lithium manganate, wherein it is preferred to, LiMn2O4 and carbon in step (1)
Quality of materials ratio is 2:1；
Described carbon material coats the preparation method of nanometer lithium manganate, wherein it is preferred to, ball grinder is agate in step (1)
Nao ball grinders；
Described carbon material coats the preparation method of nanometer lithium manganate, wherein it is preferred to, carbon material is to lead in step (1)
Electric carbon black；
Described carbon material coats the preparation method of nanometer lithium manganate, wherein it is preferred to, ball milling pearl is preferred in step (2)
For agate material ball milling pearl, and its ratio is preferably (9-10):1；
Described carbon material coats the preparation method of nanometer lithium manganate, wherein it is preferred to, step is entered in atmosphere in (3)
Row ball milling, without any protective gas；
Described carbon material coats the preparation method of nanometer lithium manganate composite, wherein it is preferred to, in step (3)
Rotational speed of ball-mill is (200-500) r/min, and Ball-milling Time is 3~24 hours；
Described conductive black coats the preparation method of nanometer lithium manganate composite, wherein it is preferred to, step (1)~
(3) ball mill is preferably high energy ball mill in, it is further preferred that ball mill is preferably high-energy planetary formula in step (1)~(3)
Ball mill；
(1) in step 1, zirconia ball grinding jar can be used.
(2) in step 1, LiMn2O4 may instead be (1-3) with carbon material mass ratio:1.
(3) in step 1, appropriate absolute ethyl alcohol can be added and carry out wet-milling or add appropriate grinding aid progress ball milling.
(4) in step 2, ball milling pearl may instead be the zirconium oxide ball milling pearl with ball grinder same material, material ratio and ball milling pearl
Particle diameter proportioning is adjusted.
(5) ball milling may instead be in nitrogen, argon gas protective gas and carry out ball milling in air in step 3.
(6) Ball-milling Time may instead be 2-24h in step 3.
(7) step 2 may instead be the mode ground in mortar with ball mill ball milling in step 3.
Embodiment 1, prepare conductive black cladding nanometer lithium manganate composite, comprise the following steps that：
Step 1：Weigh 808mg spinel lithium manganates (LiMn2O4) and 404mg conductive blacks (super P) be placed in 50ml agates
In Nao ball grinders；
Step 2：Take a diameter of 3,15mm ball millings pearl, it is a diameter of 1,8mm ball millings pearl, a diameter of 2,6mm ball millings pearl, straight
Footpath is that 10,5mm ball millings pearl is placed in above-mentioned ball grinder；
Step 3：The good ball milling cover lid of above-mentioned dispensing is sealed and is installed on high energy ball mill and carries out ball milling, rotating speed is
450rmp/min, the time is 6h.Conductive black cladding nanometer lithium manganate composite powder is obtained after the completion of ball milling.
Embodiment 2, conductive black and graphene coated nanometer lithium manganate composite are prepared, comprised the following steps that：
Step 1：Weigh 808mg spinel lithium manganates (LiMn2O4), 202mg conductive blacks (super P), 202mg graphite
Alkene powder is placed in 50ml agate jars；
Step 2：Take a diameter of 3,15mm ball millings pearl, it is a diameter of 1,8mm ball millings pearl, a diameter of 2,6mm ball millings pearl, straight
Footpath is that 10,5mm ball millings pearl is placed in above-mentioned ball grinder；
Step 3：The good ball milling cover lid of above-mentioned dispensing is sealed and is installed on high energy ball mill and carries out ball milling, rotating speed is
550rmp/min, the time is 6h.Conductive black and graphene coated nanometer lithium manganate composite powder are obtained after the completion of ball milling.
Embodiment 3, prepare conductive black cladding nanometer lithium manganate composite, comprise the following steps that：
Step 1：Weigh 600mg spinel lithium manganates (LiMn2O4) and 200mg conductive blacks (super P) be placed in agate and grind
In alms bowl.
Step 2：Above-mentioned powder is ground 1h in mortar so that material obtains conductive black after being fully pulverized and mixed
Coat nanometer lithium manganate composite powder.
Embodiment 4, conductive black cladding nanometer lithium manganate composite make organic system anode material for lithium-ion batteries, specifically
Step is as follows：
Step 1：90mg carbon-coated nano LiMn2O4s composite, 10mg binding agents PVDF are weighed respectively is placed in 10ml beakers
In, a certain amount of NMP, magnetic agitation 12h are added, is allowed to well mixed, obtains lithium ion battery anode glue size.
Step 2：Obtained slurry in step 1 is evenly applied on aluminium foil, manganese is made in 100 degrees Celsius of drying in lower 6 hours
Sour lithium electrode.
Step 3：Electrode in step 2 is cut into diameter 10mm circular pole piece, weighs and calculates active material matter on pole piece
Amount.
Step 4：Pole piece in step 3 is made into working electrode, makees, to electrode, to protect in argon atmosphere using metal lithium sheet
Button cell is assembled into glove box.
Step 5：Battery packaged in step 4 is taken out and 24h is stood.
Step 6：By the button cell stood in step 5 on blue electric charge-discharge test instrument, to its chemical property
Tested.
Embodiment 5, conductive black cladding nanometer lithium manganate composite make water system hybrid capacitors, and specific steps are such as
Under：
Step 1：The thick nickel foams of 1mm are cut into 10mm*20mm sizes, respectively with acetone, watery hydrochloric acid, deionized water successively
60 DEG C of dry 6h in vacuum drying chamber are placed in after being cleaned, are subsequently used as collector.
Step 2：Weigh 90mg conductive blacks cladding nanometer lithium manganate composite, 16.7mg mass fractions for 60% it is poly-
Tetrafluoroethene (PTFE) aqueous solution binding agent, i.e. active material are 9 with binding agent mass ratio:1；In the small beaker for pouring into 10ml,
Plus a certain amount of alcohol, magnetic agitation 1h, it is allowed to well mixed, obtains mixed capacitor anode sizing agent.
Step 3：Slurry in step 2 is uniformly coated on to foam nickel surface dried in step 1, coated area is
10*10mm.12h is dried in 100 DEG C of vacuum environment and removes alcohol and aqueous solvent, keeps vacuum state to treat that temperature is down to 40 DEG C
It can be taken out when following, the pole piece prepared.
Step 4：The 1mol/L lithium sulfate aqueous solution is prepared, electrolyte is used as.
Step 5：Make reference electrode, platinum electrode using saturated calomel electrode as to obtained pole piece in electrode, step 3 to make
Three-electrode system is constituted for working electrode to be placed in electrolytic cell, the electrolyte prepared in step 4 is added, and electrolyte will not have work
Make electrode and be applied region.
Step 6：Carry out cyclic voltammetric and constant current charge-discharge test, analysis of material chemical property.
The preferred embodiment of the application is the foregoing is only, the application is not limited to, for the skill of this area
For art personnel, the application can have various modifications and variations.It is all within spirit herein and principle, made any repair
Change, equivalent substitution, improvement etc., should be included within the protection domain of the application.
Claims (10)
1. application of the nano-scale carbon material in ball-milling method prepares carbon coating spinel lithium manganate nano composite material.
2. a kind of carbon coating spinel lithium manganate nano composite material, it is characterised in that the composite is by following parts by weight
Several raw material compositions：1-3 parts of micron order LiMn2O4s, 1 part of nano-scale carbon material, the LiMn2O4 are evenly coated at one with carbon material
Rise.
3. composite as claimed in claim 2, it is characterised in that the particle diameter of the composite is 20nm~2000nm.
4. composite as claimed in claim 2, it is characterised in that the LiMn2O4 includes spherical, octahedral build business and used
The one or more of spinel lithium manganate；
Or the carbon material is the one or more in conductive black, graphene, CNT, carbon fiber, electrically conductive ink.
5. a kind of preparation method of carbon coating spinel lithium manganate nano composite material, it is characterised in that including：
By micron order LiMn2O4, nano-scale carbon material be well mixed, ball milling, the nano combined material of carbon coating spinel lithium manganate is produced
Material.
6. method as claimed in claim 5, it is characterised in that the condition of the ball milling is：Ratio of grinding media to material 9~10:1st, rotating speed
200-580r/min, time 2-24h；
Or the ball milling uses nonmetallic ball grinder and nonmetallic ball milling pearl, preferably agate jar and agate ball milling pearl, its
Middle the small ball's diameter 2-15mm, spherical tank volume 50-200ml；
Or the ball milling uses high energy ball mill, preferably planetary ball mill.
7. method as claimed in claim 5, it is characterised in that the ball milling is carried out at room temperature.
8. carbon coating spinel lithium manganate nano composite material prepared by the method described in claim any one of 5-7.
9. a kind of preparation method of carbon coating spinel lithium manganate nano composite material electrode, it is characterised in that including：
By micron order LiMn2O4, nano-scale carbon material be well mixed, ball milling, the nano combined material of carbon coating spinel lithium manganate is obtained
Material；
Using above-mentioned carbon coating spinel lithium manganate nano composite material as active material, with binding agent, solvent complex, it must apply
Material；
Above-mentioned coating is coated on basal electrode, produced.
10. claim 2-4 or the carbon coating spinel lithium manganate nano composite material described in 7 any one are preparing electrode, lithium
Applied in ion battery, hybrid super capacitor.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710442178.5A CN107275606B (en) | 2017-06-13 | 2017-06-13 | Carbon-coated spinel lithium manganate nanocomposite and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710442178.5A CN107275606B (en) | 2017-06-13 | 2017-06-13 | Carbon-coated spinel lithium manganate nanocomposite and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107275606A true CN107275606A (en) | 2017-10-20 |
| CN107275606B CN107275606B (en) | 2020-03-17 |
Family
ID=60067162
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710442178.5A Active CN107275606B (en) | 2017-06-13 | 2017-06-13 | Carbon-coated spinel lithium manganate nanocomposite and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107275606B (en) |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108199013A (en) * | 2017-12-06 | 2018-06-22 | 欣旺达电子股份有限公司 | Carbon coating ternary material and preparation method thereof |
| CN108232131A (en) * | 2017-12-06 | 2018-06-29 | 欣旺达电子股份有限公司 | Metal fluoride cladding ternary material and preparation method thereof |
| CN108470901A (en) * | 2018-05-29 | 2018-08-31 | 山东大学 | A kind of carbon nanotube LiMn2O4 nanocomposite and preparation method and application |
| CN109390576A (en) * | 2018-12-05 | 2019-02-26 | 长沙矿冶研究院有限责任公司 | A kind of preparation method of the nickelic tertiary cathode material of carbon coating |
| CN110233266A (en) * | 2019-07-02 | 2019-09-13 | 宁夏汉尧石墨烯储能材料科技有限公司 | A kind of preparation method of graphene modification lithium-ion battery tertiary cathode material |
| CN110277554A (en) * | 2019-03-22 | 2019-09-24 | 北方奥钛纳米技术有限公司 | Positive electrode and positive plate and preparation method thereof, lithium ion battery |
| CN111403739A (en) * | 2020-03-19 | 2020-07-10 | 湖北容百锂电材料有限公司 | Nickel-cobalt-manganese acid lithium battery cell positive electrode active material, aluminum shell battery cell and manufacturing method thereof |
| CN111740085A (en) * | 2020-06-19 | 2020-10-02 | 贵州梅岭电源有限公司 | Coating modification method of lithium-rich manganese-based positive electrode material |
| CN112186158A (en) * | 2020-09-28 | 2021-01-05 | 蜂巢能源科技有限公司 | Positive electrode composite material and preparation method and application thereof |
| CN115490266A (en) * | 2022-09-27 | 2022-12-20 | 安徽博石高科新材料股份有限公司 | Preparation method of carbon-coated lithium manganate composite material |
| CN115520908A (en) * | 2022-09-23 | 2022-12-27 | 长沙学院 | Base metal ion doped lithium manganate cathode material and preparation method and application thereof |
| CN116130623A (en) * | 2022-12-20 | 2023-05-16 | 湖南法恩莱特新能源科技有限公司 | Graphene lithium battery composite material and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103872287A (en) * | 2014-03-20 | 2014-06-18 | 重庆工商大学 | Composite positive electrode material of graphene and lithium iron phosphate battery and preparation method thereof |
| CN105047917A (en) * | 2015-06-25 | 2015-11-11 | 中国航空工业集团公司北京航空材料研究院 | Preparation method of lithium iron phosphate battery cathode material |
| CN105226267B (en) * | 2015-08-25 | 2017-07-11 | 武汉理工大学 | Three dimensional carbon nanotubes modification spinel nickel lithium manganate material and its preparation method and application |
-
2017
- 2017-06-13 CN CN201710442178.5A patent/CN107275606B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103872287A (en) * | 2014-03-20 | 2014-06-18 | 重庆工商大学 | Composite positive electrode material of graphene and lithium iron phosphate battery and preparation method thereof |
| CN105047917A (en) * | 2015-06-25 | 2015-11-11 | 中国航空工业集团公司北京航空材料研究院 | Preparation method of lithium iron phosphate battery cathode material |
| CN105226267B (en) * | 2015-08-25 | 2017-07-11 | 武汉理工大学 | Three dimensional carbon nanotubes modification spinel nickel lithium manganate material and its preparation method and application |
Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108199013B (en) * | 2017-12-06 | 2021-02-12 | 欣旺达电子股份有限公司 | Carbon-coated ternary material and preparation method thereof |
| CN108232131A (en) * | 2017-12-06 | 2018-06-29 | 欣旺达电子股份有限公司 | Metal fluoride cladding ternary material and preparation method thereof |
| CN108199013A (en) * | 2017-12-06 | 2018-06-22 | 欣旺达电子股份有限公司 | Carbon coating ternary material and preparation method thereof |
| CN108470901A (en) * | 2018-05-29 | 2018-08-31 | 山东大学 | A kind of carbon nanotube LiMn2O4 nanocomposite and preparation method and application |
| CN108470901B (en) * | 2018-05-29 | 2020-09-25 | 山东大学 | Carbon nanotube lithium manganate nanocomposite and preparation method and application thereof |
| CN109390576A (en) * | 2018-12-05 | 2019-02-26 | 长沙矿冶研究院有限责任公司 | A kind of preparation method of the nickelic tertiary cathode material of carbon coating |
| CN110277554A (en) * | 2019-03-22 | 2019-09-24 | 北方奥钛纳米技术有限公司 | Positive electrode and positive plate and preparation method thereof, lithium ion battery |
| CN110277554B (en) * | 2019-03-22 | 2022-04-19 | 北方奥钛纳米技术有限公司 | Positive electrode material, positive plate, preparation methods of positive electrode material and positive plate, and lithium ion battery |
| CN110233266A (en) * | 2019-07-02 | 2019-09-13 | 宁夏汉尧石墨烯储能材料科技有限公司 | A kind of preparation method of graphene modification lithium-ion battery tertiary cathode material |
| CN111403739A (en) * | 2020-03-19 | 2020-07-10 | 湖北容百锂电材料有限公司 | Nickel-cobalt-manganese acid lithium battery cell positive electrode active material, aluminum shell battery cell and manufacturing method thereof |
| CN111740085A (en) * | 2020-06-19 | 2020-10-02 | 贵州梅岭电源有限公司 | Coating modification method of lithium-rich manganese-based positive electrode material |
| CN111740085B (en) * | 2020-06-19 | 2022-02-01 | 贵州梅岭电源有限公司 | Coating modification method of lithium-rich manganese-based positive electrode material |
| CN112186158A (en) * | 2020-09-28 | 2021-01-05 | 蜂巢能源科技有限公司 | Positive electrode composite material and preparation method and application thereof |
| CN115520908A (en) * | 2022-09-23 | 2022-12-27 | 长沙学院 | Base metal ion doped lithium manganate cathode material and preparation method and application thereof |
| CN115490266A (en) * | 2022-09-27 | 2022-12-20 | 安徽博石高科新材料股份有限公司 | Preparation method of carbon-coated lithium manganate composite material |
| CN116130623A (en) * | 2022-12-20 | 2023-05-16 | 湖南法恩莱特新能源科技有限公司 | Graphene lithium battery composite material and preparation method and application thereof |
| CN116130623B (en) * | 2022-12-20 | 2024-03-19 | 湖南法恩莱特新能源科技有限公司 | Graphene lithium battery composite material and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107275606B (en) | 2020-03-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107275606A (en) | A kind of carbon coating spinel lithium manganate nano composite material and preparation method and application | |
| CN109599551B (en) | Doped multilayer core-shell silicon-based composite material for lithium ion battery and preparation method thereof | |
| Yang et al. | Bismuth Nanoparticles Embedded in Carbon Spheres as Anode Materials for Sodium/Lithium‐Ion Batteries | |
| CN100530780C (en) | Composite lithium titanate electrode material and preparation method thereof | |
| CN102468485B (en) | Lithium titanate composite material, preparation method thereof, and application thereof | |
| Li et al. | SnO 2–carbon–RGO heterogeneous electrode materials with enhanced anode performances in lithium ion batteries | |
| CN103531758B (en) | Nano metal tin and composite cathode material of silicon/carbon/graphite and preparation method thereof | |
| CN105883940B (en) | Preparation method of block NiS2 and application of block NiS2 to sodium-ion battery | |
| CN102208614B (en) | Method for preparing lithium ion battery cathode material coated iron sesquioxide | |
| Feng et al. | Low-cost SiO-based anode using green binders for lithium ion batteries | |
| CN109037636A (en) | A kind of preparation method of SiO/ carbon graphite composite negative pole material | |
| WO2011009231A1 (en) | Method for preparing carbon-coated positive material of lithium ion battery | |
| CN105870384A (en) | Nitrogen-doped carbon nanotube/manganese-cobalt oxide nano composite material for lithium battery electrodes | |
| CN105449178B (en) | A kind of preparation method of nano lithium manganese phosphate of lithium/graphene/carbon composite material | |
| CN107221654A (en) | A kind of three-dimensional porous nest like silicon-carbon composite cathode material and preparation method thereof | |
| CN102856553A (en) | Preparation method of hydrothermal synthesis carbon coated lithium iron phosphate | |
| CN106356515A (en) | Preparation method of silicon oxide composite material | |
| CN112563038A (en) | CoMoO4/Ti3C2Nano composite particle and preparation method and application thereof | |
| Wang et al. | Few‐Layer MoS2 Nanosheets Encapsulated in N‐Doped Carbon Hollow Spheres as Long‐Life Anode Materials for Lithium‐Ion Batteries | |
| CN104577063B (en) | A kind of WS2 MoS2 C composite negative pole materials and preparation method thereof | |
| CN107093710B (en) | Two-coat lithium ion battery negative material and preparation method thereof and lithium ion battery | |
| Gao et al. | Influencing factors of low-and high-temperature behavior of Co-doped Zn2SnO4–graphene–carbon nanocomposite as anode material for lithium-ion batteries | |
| CN106450186B (en) | A kind of preparation method, anode sizing agent and the application of lithium-ion battery anode material lithium manganese silicate/carbon composite | |
| CN105489868B (en) | A kind of lithium ion battery negative material, its preparation method and lithium ion battery | |
| CN105161678A (en) | Multi-layer composite titanium dioxide nanotube material for lithium battery electrode |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |