CN110165178A - A kind of anode material of lithium battery and preparation method thereof and the lithium battery comprising the positive electrode - Google Patents
A kind of anode material of lithium battery and preparation method thereof and the lithium battery comprising the positive electrode Download PDFInfo
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- CN110165178A CN110165178A CN201910439213.7A CN201910439213A CN110165178A CN 110165178 A CN110165178 A CN 110165178A CN 201910439213 A CN201910439213 A CN 201910439213A CN 110165178 A CN110165178 A CN 110165178A
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- porous carbon
- active material
- organic matter
- lithium battery
- positive electrode
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 34
- 239000010405 anode material Substances 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 47
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 47
- 239000011248 coating agent Substances 0.000 claims abstract description 37
- 238000000576 coating method Methods 0.000 claims abstract description 37
- 239000011149 active material Substances 0.000 claims abstract description 35
- 239000005416 organic matter Substances 0.000 claims abstract description 21
- 229910001338 liquidmetal Inorganic materials 0.000 claims abstract description 11
- 230000000694 effects Effects 0.000 claims abstract description 10
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 8
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 238000005245 sintering Methods 0.000 claims abstract description 6
- -1 simultaneously Substances 0.000 claims abstract description 4
- 239000000463 material Substances 0.000 claims description 26
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 claims description 20
- 239000000919 ceramic Substances 0.000 claims description 11
- 230000035484 reaction time Effects 0.000 claims description 9
- 239000011148 porous material Substances 0.000 claims description 6
- 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 claims description 5
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 claims description 5
- 239000008103 glucose Substances 0.000 claims description 5
- 229910052493 LiFePO4 Inorganic materials 0.000 claims description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 4
- 239000004202 carbamide Substances 0.000 claims description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 3
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 claims description 3
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000004411 aluminium Substances 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 229910001453 nickel ion Inorganic materials 0.000 claims description 3
- 235000021355 Stearic acid Nutrition 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 238000003763 carbonization Methods 0.000 claims description 2
- 238000005255 carburizing Methods 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 239000011258 core-shell material Substances 0.000 claims description 2
- 235000003642 hunger Nutrition 0.000 claims description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 2
- 230000037351 starvation Effects 0.000 claims description 2
- 239000008117 stearic acid Substances 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims 2
- 244000248349 Citrus limon Species 0.000 claims 2
- 235000005979 Citrus limon Nutrition 0.000 claims 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims 1
- 229910021529 ammonia Inorganic materials 0.000 claims 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims 1
- 239000003792 electrolyte Substances 0.000 abstract description 9
- 230000018044 dehydration Effects 0.000 abstract description 8
- 238000006297 dehydration reaction Methods 0.000 abstract description 8
- 239000007788 liquid Substances 0.000 abstract description 6
- 238000007086 side reaction Methods 0.000 abstract description 4
- 238000011065 in-situ storage Methods 0.000 abstract description 2
- 229910052751 metal Inorganic materials 0.000 abstract description 2
- 239000002184 metal Substances 0.000 abstract description 2
- 230000008021 deposition Effects 0.000 abstract 1
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 26
- 239000010410 layer Substances 0.000 description 16
- 239000007789 gas Substances 0.000 description 14
- 229910052786 argon Inorganic materials 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 238000010792 warming Methods 0.000 description 12
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 7
- 238000002844 melting Methods 0.000 description 6
- 230000008018 melting Effects 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 5
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 5
- 239000001099 ammonium carbonate Substances 0.000 description 5
- 238000005253 cladding Methods 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 238000003780 insertion Methods 0.000 description 2
- 230000037431 insertion Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000005955 Ferric phosphate Substances 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000005030 aluminium foil Substances 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 229940032958 ferric phosphate Drugs 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 1
- 229910000399 iron(III) phosphate Inorganic materials 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 102220043159 rs587780996 Human genes 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002344 surface layer Substances 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
- 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
- H01M4/362—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
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Composite Materials (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a kind of anode material of lithium battery and preparation method thereof with include the lithium battery of the positive electrode.The present invention is first in the coated porous carbon-coating of surface of active material, porous carbon coating active material is mixed with liquid metals organic matter afterwards, the mode of solid-liquid mixing, liquid metals organic matter is enabled equably to be wrapped in porous carbon coating surface of active material, it is reacted again by metal liquid organic matter with vapor, through high temperature sintering, dehydration so that the Al generated2O3In-situ deposition is on the hole and carbon-coating of porous carbon layer, and Al2O3It " can steadily follow closely " on porous carbon layer surface, to reach better covered effect, and active material and electrolyte can be made to separate, reduce the side reaction of positive electrode and electrolyte, simultaneously, intermediate porous carbon layer enhances the electric conductivity of positive electrode, effectively increases coulombic efficiency for the first time, cycle performance and the high rate performance of battery.
Description
Technical field
The present invention relates to field of lithium more particularly to a kind of anode material of lithium battery and preparation method thereof with comprising this just
The lithium battery of pole material.
Background technique
The electric conductivity of anode material for lithium-ion batteries is poor, so that its high rate performance is poor, it will usually coat one on its surface
Layer conductive carbon, is either added a large amount of the carbon black perhaps conductive agents such as carbon pipe but conductive carbon or homogenate when homogenate prepares pole piece
The conductive agent large specific surface area being added in the process, increases the side reaction with electrolyte, in addition, anode material for lithium-ion batteries exists
It is easy in charge and discharge process and electrolyte reacts to form one layer of stable SEI film, although the work of stable circulating battery can be played
With, but limited lithium ion in battery is also consumed, to influence the first charge discharge efficiency and cycle performance of positive electrode.
To solve the above-mentioned problems, it generallys use one layer of electrochemically stable clad to coat positive electrode, make
It obtains positive electrode and electrolyte separates, Al2O3As the ceramic layer of electronic isolation, it can play and hinder electrolyte well and lead
Side reaction between electric agent preferably coats although current atomic deposition method can be realized, its cost is excessively high, unfavorable
In actual production.
Thus it is necessary to provide a kind of more effective simple Al at low cost2O3Method for coating, be clad anode material into
One step application lays the foundation.
Summary of the invention
The purpose of the present invention is to provide a kind of anode material of lithium battery and preparation method thereof with include the positive electrode
Lithium battery, the present invention by coating one layer of porous carbon layer in surface of active material, after by porous carbon layer and liquid metals organic matter
It is uniformly mixed, is passed through the Al obtained after vapor reaction-sintered2O3The hole and carbon-coating of porous carbon layer can be relatively evenly deposited on
In, and Al2O3It can steadily " follow closely " at porous carbon layer surface (see Fig. 1).
It is specific as follows:
One of the objects of the present invention is to provide a kind of anode material of lithium battery, which is core-shell structure, core
Portion is active material, and shell portion is made of porous carbon layer and ceramic deposits, and the ceramic layer deposits are in porous carbon layer hole
Hole and carbon-coating surface.
Preferably, above-mentioned porous carbon layer with a thickness of 10nm~5 μm；More preferably 500nm~1 μm.
Preferably, above-mentioned ceramic deposits with a thickness of 1~100nm；More preferably 5~10nm.
Preferably, above-mentioned ceramic deposits are selected from Al2O3。
Preferably, above-mentioned active material is selected from nickel-cobalt-manganese ternary material (NCM), nickel cobalt aluminium ternary material (NCA), ferric phosphate
At least one of lithium (LFP), LiMn2O4 (LMO), nickel ion doped (LNMO).
Another object of the present invention is to provide the preparation methods of above-mentioned positive electrode, include the following steps:
1) it is carbonized after mixing active material, organic matter and pore creating material, obtains porous carbon coating active material；
2) under conditions of starvation, porous carbon coating active material is mixed with liquid metals organic matter, after be passed through water
Vapor reaction, sintered ceramic deposits are deposited on porous carbon coating surface of active material, obtain anode material of lithium battery.
Preferably, the mass ratio of the active material in step 1), organic matter and pore creating material is 100:(10~30): (5~
10)；More preferably 100:(15~20): (6~8).
Preferably, nickel-cobalt-manganese ternary material (NCM), nickel cobalt aluminium ternary material (NCA), LiFePO4 (LFP), LiMn2O4
(LMO), the partial size of nickel ion doped (LNMO) is 5~25 μm, it is further preferred that partial size is 10~15 μm.
Preferably, the carburizing temperature in step 1) is 400~600 DEG C；More preferably 450~550 DEG C.
Preferably, the carbonization time in step 1) is 0.5~10h；More preferably 4~8h.
Preferably, the active material, organic matter and pore creating material of step 1) in rotary furnace in mixing；Preferably, rotary furnace
Revolving speed is 5~50rpm/min.
Preferably, the organic matter in step 1) is selected from glucose, citric acid, stearic acid, inclined phthalate anhydride, O-phthalic
At least one of acid anhydrides.
Preferably, above-mentioned pore creating material is selected from least one of ammonium hydrogen carbonate, urea.
It preferably, further included obtaining porous carbon coating active material after 325 meshes in step 1).
Preferably, the mass ratio of the liquid metals organic matter and active material in step 2) is (1~2): 100；More preferably
For (1.5~1.8): 100.
Preferably, the mass ratio of vapor intake and active material is (5~10): 100；More preferably 6:100.
Preferably, the reaction time of liquid metals organic matter and vapor is 1~4h in step 2)；More preferably 1.5~
2h。
Preferably, the sintering temperature in step 2) is 800~950 DEG C；More preferably 900 DEG C.
Preferably, the sintering reaction time in step 2) is 5~10h；More preferably 6~8h.
Preferably, aforesaid liquid metallorganic is selected from trimethyl aluminium.
The present invention also provides a kind of lithium batteries, and the lithium battery pack is containing above-mentioned positive electrode.
The beneficial effects of the present invention are:
The present invention first in the coated porous carbon-coating of surface of active material, after by porous carbon coating active material and liquid gold
Belong to organic matter mixing, the mode of solid-liquid mixing enables liquid metals organic matter to be equably wrapped in porous carbon coating activity
Material surface, then reacted by metal liquid organic matter with vapor, through high temperature sintering, dehydration so that the Al generated2O3It is in situ heavy
Product is on the hole and carbon-coating of porous carbon layer, and Al2O3It can steadily " follow closely " on porous carbon layer surface, to reach better
Covered effect reduces the side reaction of positive electrode and electrolyte so that active material and electrolyte separate, meanwhile, it is also beneficial to
The insertion of lithium ion and it is embedding go out, and porous carbon layer therein also can be further improved the electric conductivity of positive electrode, thus effectively
Improve coulombic efficiency for the first time, cycle performance and the high rate performance of battery.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of anode material of lithium battery prepared by the present invention；
Fig. 2 is the positive electrode SEM figure before the embodiment of the present invention 6 coats and after cladding.
Specific embodiment
Enumerate embodiment further below with the present invention will be described in detail.It will similarly be understood that following embodiment is served only for this
Invention is further described, and should not be understood as limiting the scope of the invention, those skilled in the art are according to the present invention
Some nonessential modifications and adaptations that the principle of elaboration is made all belong to the scope of protection of the present invention.Following specific works of example
Skill parameter etc. is also only an example in OK range, i.e. those skilled in the art can do suitable model by the explanation of this paper
Interior selection is enclosed, and does not really want to be defined in hereafter exemplary specific data.
Embodiment 1
A kind of preparation method of anode material of lithium battery, includes the following steps:
1) NCM811, glucose and ammonium hydrogencarbonate are uniformly mixed in mass ratio for 100:30:10, after be put into revolving speed and be
400 DEG C are warming up in the melting down of 45rpm/min, be carbonized 8h, after be cooled to room temperature, cross 325 meshes, obtain porous carbon coating activity material
Material；
2) porous carbon coating active material being put into rotary furnace and is rotated, revolving speed 20rpm/min is passed through argon gas 2h, after
Trimethyl aluminium is squeezed into revolution furnace cavity, the mass ratio of trimethyl aluminium and NCM811 are 2:100, stir 2h, continue to be passed through argon
Vapor is simultaneously blown into cavity by gas, and the amount of being blown into of vapor and the mass ratio of NCM811 are 5:100, trimethyl aluminium and vapor
Reaction time is 2h, is continually fed into argon gas, and rotary furnace is warming up to 950 DEG C and is sintered dehydration, keeps the temperature 10h, drop naturally afterwards
It warms to room temperature, obtains anode material of lithium battery.
Embodiment 2
A kind of preparation method of anode material of lithium battery, includes the following steps:
1) NCM811, glucose and ammonium hydrogencarbonate are uniformly mixed in mass ratio for 100:20:8, after be put into revolving speed and be
600 DEG C are warming up in the melting down of 45rpm/min, be carbonized 6h, after be cooled to room temperature, cross 325 meshes, obtain porous carbon coating activity material
Material；
2) porous carbon coating active material being put into rotary furnace and is rotated, revolving speed 20rpm/min is passed through nitrogen 2h, after
Trimethyl aluminium is squeezed into revolution furnace cavity, the mass ratio of trimethyl aluminium and NCM811 are 1.5:100, stir 1h, continue to be passed through
Vapor is simultaneously blown into cavity by nitrogen, and the amount of being blown into of vapor and the mass ratio of NCM811 are 6:100, trimethyl aluminium and vapor
Reaction time be 1.5h, be continually fed into nitrogen, and rotary furnace is warming up to 900 DEG C and is sintered dehydration, keep the temperature 10h, it is rear oneself
It so is cooled to room temperature, obtains anode material of lithium battery.
Embodiment 3
A kind of preparation method of anode material of lithium battery, includes the following steps:
1) NCM811, citric acid and ammonium hydrogencarbonate are uniformly mixed in mass ratio for 100:25:8, after be put into revolving speed and be
500 DEG C are warming up in the melting down of 40rpm/min, be carbonized 5h, after be cooled to room temperature, cross 325 meshes, obtain porous carbon coating activity material
Material；
2) porous carbon coating active material being put into rotary furnace and is rotated, revolving speed 15rpm/min is passed through nitrogen 2h, after
Trimethyl aluminium is squeezed into revolution furnace cavity, the mass ratio of trimethyl aluminium and NCM811 are 2:100, stir 2h, continue to be passed through nitrogen
Vapor is simultaneously blown into cavity by gas, and the amount of being blown into of vapor and the mass ratio of NCM811 are 8:100, trimethyl aluminium and vapor
Reaction time is 2h, is continually fed into nitrogen, and rotary furnace is warming up to 800 DEG C and is sintered dehydration, keeps the temperature 8h, rear Temperature fall
To room temperature, anode material of lithium battery is obtained.
Embodiment 4
A kind of preparation method of anode material of lithium battery, includes the following steps:
1) NCM811, citric acid and urea are uniformly mixed in mass ratio for 100:20:8, after be put into revolving speed be 35rpm/
600 DEG C are warming up in the melting down of min, be carbonized 4h, after be cooled to room temperature, cross 325 meshes, obtain porous carbon coating active material；
2) porous carbon coating active material being put into rotary furnace and is rotated, revolving speed 15rpm/min is passed through argon gas 1h, after
Trimethyl aluminium is squeezed into revolution furnace cavity, the mass ratio of trimethyl aluminium and NCM811 are 1.5:100, stir 2h, continue to be passed through
Vapor is simultaneously blown into cavity by argon gas, and the amount of being blown into of vapor and the mass ratio of NCM811 are 8:100, trimethyl aluminium and vapor
Reaction time be 2h, be continually fed into argon gas, and rotary furnace is warming up to 900 DEG C and is sintered dehydration, keep the temperature 6h, afterwards drop naturally
It warms to room temperature, obtains anode material of lithium battery.
Embodiment 5
A kind of preparation method of anode material of lithium battery, includes the following steps:
1) NCM811, hard acid ester and Ammonium bicarbonate food grade are uniformly mixed in mass ratio for 100:30:6, after be put into revolving speed and be
400 DEG C are warming up in the melting down of 45rpm/min, be carbonized 6h, after be cooled to room temperature, cross 325 meshes, obtain porous carbon coating activity material
Material；
2) porous carbon coating active material being put into rotary furnace and is rotated, revolving speed 20rpm/min is passed through argon gas 2h, after
Trimethyl aluminium is squeezed into revolution furnace cavity, the mass ratio of trimethyl aluminium and NCM811 are 1:100, stir 2h, continue to be passed through argon
Vapor is simultaneously blown into cavity by gas, and the amount of being blown into of vapor and the mass ratio of NCM811 are 6:100, trimethyl aluminium and vapor
Reaction time is 2h, is continually fed into argon gas, and rotary furnace is warming up to 950 DEG C and is sintered dehydration, keeps the temperature 8h, rear Temperature fall
To room temperature, anode material of lithium battery is obtained.
Embodiment 6
A kind of preparation method of anode material of lithium battery, includes the following steps:
1) NCM811, glucose and urea are uniformly mixed in mass ratio for 100:20:5, after be put into revolving speed be 45rpm/
400 DEG C are warming up in the melting down of min, be carbonized 6h, after be cooled to room temperature, cross 325 meshes, obtain porous carbon coating active material；
2) porous carbon coating active material is put into rotary furnace and is rotated, revolving speed 8rpm/min is passed through argon gas 2h, after will
Trimethyl aluminium is squeezed into cavity, and the mass ratio of trimethyl aluminium and NCM811 is 1:100, stirs 2h, continues to be passed through argon gas and by water
Steam is blown into cavity, and the amount of being blown into of vapor and the mass ratio of NCM811 are 8:100, the reaction time of trimethyl aluminium and vapor
For 2h, be continually fed into argon gas, and rotary furnace is warming up to 900 DEG C and is sintered dehydration, keep the temperature 6h, after be naturally cooling to room temperature,
Obtain anode material of lithium battery.
Comparative example 1
Use commercially available carbon coating NCM811 for positive electrode, D50=16 μm of granularity.
Comparative example 2
Preparation method is with embodiment 6, the difference is that only carrying out porous carbon coating.
Comparative example 3
Preparation method is with embodiment 6, the difference is that only carrying out Al without porous carbon coating2O3Cladding.
1, SEM is tested:
Positive electrode sample before embodiment 6 is coated and after cladding carries out SEM test, as a result sees Fig. 2；
As shown in Figure 2: the positive electrode surface before cladding can see apparent lattice fringe, and after cladding just
The material surface lattice fringe in pole disappears instead the more uniform unformed substance of a layer thickness (dotted line part in figure
Point), which is agraphitic carbon and Al2O3Clad, that is, the shell portion of positive electrode prepared by the present invention.
2, performance test:
It mixes, adds by the mass ratio of the positive electrode of Examples 1 to 6 and comparative example 1~3, SP, PVDF=95.5:2:2.5
Enter suitable NMP as dispersing agent and be tuned into slurry, is coated on aluminium foil afterwards, and vacuum dried, roll-in, positive plate is made, gold
Belong to lithium to be used as to electrode, use the tri- component mixed solvent of LiPF6 of 1mol/L (EC, DMC, EMC are that 1:1:1 is mixed by volume)
Electrolyte, use microporous polypropylene membrane for diaphragm, full of argon gas glove box in be assembled into CR2016 type button cell, will
The button cell carries out charge-discharge test, test condition in Shenzhen Xin Wei Co., Ltd Neware battery test system are as follows: room
Under temperature, 0.1C constant current charge-discharge, charging/discharging voltage is limited in 3.0~4.3V, and long circulating tests 1C charging, 1C electric discharge, charge and discharge
Voltage is limited in 3.0~4.3V, as a result see the table below 1:
Table 1
As shown in Table 1: the circulation volume conservation rate of the positive electrode of embodiment all has relative to comparative example significantly to be mentioned
Height, this illustrates that double-coating of the invention is more stable, this is because Al2O3Energy " nail " realizes more stable packet in porous carbon
It covers, and for coulombic efficiency for the first time, the effect of embodiment is also better than the effect of comparative example, this illustrates that double-coating of the invention exists
Guarantee insertion and abjection that lithium ion can also be effectively ensured under the premise of cycle performance, although improving only 1 relative to comparative example
~3% or so, but the result already belongs to and obtains biggish breakthrough, because up being mentioned again on the basis of coulombic efficiency is higher for the first time
There are biggish technical difficulty for height.
Claims (10)
1. a kind of anode material of lithium battery, it is characterised in that: the positive electrode is core-shell structure, and core portion is active material,
Shell portion is made of porous carbon layer and ceramic deposits, and the ceramic deposits are deposited on the porous carbon layer hole and carbon-coating table
Face.
2. positive electrode according to claim 1, it is characterised in that: the porous carbon layer with a thickness of 10nm~5 μm；It is excellent
Selection of land, the ceramic deposits with a thickness of 1~100nm.
3. positive electrode according to claim 1 or 2, it is characterised in that: the ceramic deposits are selected from Al2O3；It is preferred that
Ground, the active material is in nickel-cobalt-manganese ternary material, nickel cobalt aluminium ternary material, LiFePO4, LiMn2O4, nickel ion doped
It is at least one.
4. the preparation method of positive electrode described in claims 1 to 3 any one, characterized by the following steps:
1) it is carbonized after mixing active material, organic matter and pore creating material, obtains porous carbon coating active material；
2) under conditions of starvation, porous carbon coating active material is mixed with liquid metals organic matter, after be passed through vapor
Reaction, sintered ceramic deposits are deposited on porous carbon coating surface of active material, obtain anode material of lithium battery.
5. the preparation method according to claim 4, it is characterised in that: active material described in step 1), organic matter and make
The mass ratio of hole agent is 100:10~30:5~10；Preferably, the carburizing temperature in step 1) is 400~600 DEG C；Preferably,
Carbonization time is 0.5~10h.
6. the preparation method according to claim 4, it is characterised in that: organic matter described in step 1) is selected from glucose, lemon
At least one of lemon acid, stearic acid, inclined phthalate anhydride, phthalic anhydride；Preferably, the pore creating material is selected from bicarbonate
At least one of ammonia, urea.
7. the preparation method according to claim 4, it is characterised in that: liquid metals organic matter described in step 2) and activity
The mass ratio of material is 1~2:100；Preferably, the mass ratio of vapor intake and active material is 5~10:100；It is preferred that
Ground, the reaction time of liquid metals organic matter and vapor is 1~4h in step 2).
8. the preparation method according to claim 4, it is characterised in that: the sintering temperature in step 2) is 800~950 DEG C；
Preferably, sintering time is 5~10h.
9. according to preparation method described in claim 4~8 any one, it is characterised in that: the liquid metals organic matter choosing
From trimethyl aluminium.
10. a kind of lithium battery, it is characterised in that: the lithium battery pack is containing positive material described in 3 any one of claims 1 to 3
Material.
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