CN107195899A - A kind of method of anode material for lithium-ion batteries coating modification - Google Patents
A kind of method of anode material for lithium-ion batteries coating modification Download PDFInfo
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- CN107195899A CN107195899A CN201710265912.5A CN201710265912A CN107195899A CN 107195899 A CN107195899 A CN 107195899A CN 201710265912 A CN201710265912 A CN 201710265912A CN 107195899 A CN107195899 A CN 107195899A
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- lithium
- positive electrode
- anode material
- ion batteries
- coating modification
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- 239000011248 coating agent Substances 0.000 title claims abstract description 60
- 238000000576 coating method Methods 0.000 title claims abstract description 60
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 32
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 239000010405 anode material Substances 0.000 title claims abstract description 28
- 230000004048 modification Effects 0.000 title claims abstract description 27
- 238000012986 modification Methods 0.000 title claims abstract description 27
- 238000000034 method Methods 0.000 title claims abstract description 21
- 239000000463 material Substances 0.000 claims abstract description 27
- 238000000227 grinding Methods 0.000 claims abstract description 21
- 238000000967 suction filtration Methods 0.000 claims abstract description 19
- 150000003608 titanium Chemical class 0.000 claims abstract description 7
- 239000003960 organic solvent Substances 0.000 claims abstract description 5
- KKEYFWRCBNTPAC-UHFFFAOYSA-N terephthalic acid group Chemical group C(C1=CC=C(C(=O)O)C=C1)(=O)O KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 60
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 54
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 30
- 239000011259 mixed solution Substances 0.000 claims description 22
- 239000012065 filter cake Substances 0.000 claims description 18
- 239000007788 liquid Substances 0.000 claims description 18
- 239000000843 powder Substances 0.000 claims description 18
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 17
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 16
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 16
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 10
- 235000019253 formic acid Nutrition 0.000 claims description 9
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 8
- QJKSCTQFTLWJLX-UHFFFAOYSA-N C(C1=CC=C(C(=O)O)C=C1)(=O)O.NNC(NN)=O Chemical compound C(C1=CC=C(C(=O)O)C=C1)(=O)O.NNC(NN)=O QJKSCTQFTLWJLX-UHFFFAOYSA-N 0.000 claims description 8
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000011572 manganese Substances 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 239000012621 metal-organic framework Substances 0.000 abstract description 30
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract description 9
- 229910052751 metal Inorganic materials 0.000 abstract description 4
- 239000002184 metal Substances 0.000 abstract description 4
- 229910052744 lithium Inorganic materials 0.000 abstract description 3
- 239000004408 titanium dioxide Substances 0.000 abstract description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 2
- 238000001035 drying Methods 0.000 abstract 1
- 150000003839 salts Chemical class 0.000 abstract 1
- 229910002991 LiNi0.5Co0.2Mn0.3O2 Inorganic materials 0.000 description 40
- 238000006243 chemical reaction Methods 0.000 description 33
- 239000000243 solution Substances 0.000 description 32
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 16
- 238000001354 calcination Methods 0.000 description 16
- 239000003814 drug Substances 0.000 description 16
- 239000004570 mortar (masonry) Substances 0.000 description 16
- 230000014759 maintenance of location Effects 0.000 description 15
- 238000013019 agitation Methods 0.000 description 13
- 239000010936 titanium Substances 0.000 description 9
- 238000002156 mixing Methods 0.000 description 8
- 238000005253 cladding Methods 0.000 description 7
- 239000000126 substance Substances 0.000 description 5
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 5
- 229910032387 LiCoO2 Inorganic materials 0.000 description 4
- 229910052493 LiFePO4 Inorganic materials 0.000 description 4
- 229910002993 LiMnO2 Inorganic materials 0.000 description 4
- 229910012752 LiNi0.5Mn0.5O2 Inorganic materials 0.000 description 4
- 229910015915 LiNi0.8Co0.2O2 Inorganic materials 0.000 description 4
- 229910003005 LiNiO2 Inorganic materials 0.000 description 4
- 239000002245 particle Substances 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- 238000002604 ultrasonography Methods 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 239000000320 mechanical mixture Substances 0.000 description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- NLQMSBJFLQPLIJ-UHFFFAOYSA-N (3-methyloxetan-3-yl)methanol Chemical compound OCC1(C)COC1 NLQMSBJFLQPLIJ-UHFFFAOYSA-N 0.000 description 1
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 1
- IJMWOMHMDSDKGK-UHFFFAOYSA-N Isopropyl propionate Chemical compound CCC(=O)OC(C)C IJMWOMHMDSDKGK-UHFFFAOYSA-N 0.000 description 1
- QOSMNYMQXIVWKY-UHFFFAOYSA-N Propyl levulinate Chemical compound CCCOC(=O)CCC(C)=O QOSMNYMQXIVWKY-UHFFFAOYSA-N 0.000 description 1
- QSNQXZYQEIKDPU-UHFFFAOYSA-N [Li].[Fe] Chemical compound [Li].[Fe] QSNQXZYQEIKDPU-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- XEVRDFDBXJMZFG-UHFFFAOYSA-N carbonyl dihydrazine Chemical compound NNC(=O)NN XEVRDFDBXJMZFG-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000009193 crawling Effects 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003411 electrode reaction Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- -1 titanium ions Chemical class 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229920000428 triblock copolymer Polymers 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- 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)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The present invention discloses a kind of method of anode material for lithium-ion batteries coating modification, belongs to new energy anode material of lithium battery technical field.The method of the invention is：Positive electrode is uniformly mixed into the solution of template, organic solvent, part and organic titanium salt, then uniform solution mixed above is transferred in autoclave again, at high temperature under high pressure, organic metal salt and part are self-assembled into the presence of template and are uniformly coated on positive electrode surface for metal-organic framework materials (MOFs).It will be calcined again after resulting product suction filtration, drying and grinding, that is, obtain the last anode material for lithium-ion batteries for having coated poriferous titanium dioxide.The anode material for lithium-ion batteries that the method for the invention is prepared can improve the high temperature performance of battery, and constitutionally stable coated by titanium dioxide can significantly improve the cyclical stability of positive electrode on positive electrode surface.
Description
Technical field
The present invention relates to be that a kind of coated using metal-organic framework materials (MOFs) to anode material for lithium-ion batteries is changed
The method of property, belongs to new energy anode material of lithium battery technical field.
Background technology
Presently used anode material for lithium-ion batteries all has the shortcomings that some are intrinsic, for example, circulate under high voltages
Undergo phase transition and cause cyclical stability bad, electronic conductivity is low and Li/Ni mixings cause high rate performance poor, easily with air
CO2And H20, which reacts, generates LiCO3And LiOH, cause high temperature inflatable and cycle performance to decline, Ni under the de- lithium state of height4+'s
Strong oxidizing property tends to be reduced into Ni3+And discharge O2Cause heat endurance poor, for these problems, it has been found that ion can be passed through
Doping, Surface coating and the chemical property using the measures such as electrolysis additive improvement positive electrode.
Because electrode reaction occurs in electrode/electrolyte interface, so changing an effective ways of positive electrode performance
Exactly the surface of material is coated.Cladding can improve the reversible specific capacity of material, cycle performance and high rate performance, and
Hot property.But influence of the cladding to electrode performance is highly dependent on performance, content, heat treatment condition of clad etc..For
Positive electrode is coated with three kinds of traditional methods：(1) directly mechanical mixture is coated：Direct mechanical mixture can cause crawling
Even, also some region surfaces exposure, the part of cladding also occurs that coating particle is reunited.(2) chemical vapor infiltration (CVD)：
Although the reason for continuous the coating positive electrode of energy densification is due to method causes those non-conductive and non-porous material
Expect that also coating is on surface.(3) coprecipitation (co-ppt)：Equally inevitably there is the group of coating particle in coprecipitation
Poly-, cladding is uneven, and coating crack.
The content of the invention
It is organic using metal it is an object of the invention to provide a kind of method of anode material for lithium-ion batteries coating modification
Framework material (MOFs) allows positive electrode to enter porous metal organic bone anode material for lithium-ion batteries coating coating modification
In the space of frame material (MOFs), it is uniform that the central metal titanium ions of the metal-organic framework materials after sintering just generates titanium oxide
Be coated on positive electrode surface, specifically include following steps：
(1) at room temperature, it is 1 according to mol ratio by organic titanium salt, part, template and organic solvent：(1.5~3)：(15~
30)：The ratio of (40 ~ 60) is made into mixed solution, then anode material for lithium-ion batteries is added in mixed solution, makes lithium-ion electric
Pond positive electrode is well mixed with mixed solution obtains mixture；Wherein, anode material for lithium-ion batteries and organic titanium salt rub
You are than being 100：(0.5~3.0)；
(2) mixture for obtaining step (1) is added and is transferred in autoclave, and 12 are reacted at a temperature of 120 ~ 200 DEG C
~36h；
(3) the turbid liquid after the completion of being reacted in step (2) is subjected to suction filtration, 300 mesh sieves, grinding is crossed after filter cake vacuum drying, grinding
Powder afterwards, calcines 2~12 hours at a temperature of 200~580 DEG C, that is, obtains the lithium ion cell positive finally coated
Material.
It is preferred that, (1) described template is methanol (CH in step of the present invention3OH), formic acid (HCOOH) or P123(polycyclic
Oxidative ethane-PPOX-PEO triblock copolymer C5H10O2)。
It is preferred that, organic solvent described in step (1) of the present invention is dimethylformamide (C3H7NO)。
It is preferred that, part described in step (1) of the present invention is terephthalic acid (TPA) (HOOCC6H4) or diaminourea is to benzene COOH
Dioctyl phthalate (C8H7NO4)。
It is preferred that, step (1) the of the present invention organic titanium salt is tetrabutyl titanate (C16H36O4Ti), butyl titanate
(C16H36O4Ti), butyl titanate (C16H36O4Ti), isopropyl titanate (C12H28O4Ti), isopropyl titanate (Ti4(OCH3)16) or
Titanium tetraisopropylate (C12H28O4Ti)。
Anode material for lithium-ion batteries of the present invention can be the anode material for lithium-ion batteries and phosphoric acid of any system
Iron lithium anode material, preferably ternary nickel cobalt manganese anode material for lithium-ion batteries LiNi x Co y Mn z O2, wherein, 0≤x≤1,0≤y≤
1,0≤z≤1, x+y+z=1).
Beneficial effects of the present invention：
(1) coating particles can be uniformly coated on positive electrode surface by the method for the invention, with not reuniting, tight,
The features such as stable and flawless；Also, because titanium dioxide is zero strain material, under the high/low temperature cycling condition of battery and send out
During raw reaction, Volume Changes very little, so structure is very stable, will not avalanche.Therefore lithium ion cell positive is drastically increased
The chemical property of material, beneficial to the commercialization and popularization of lithium ion battery.
(2) metal-organic framework materials (MOFs) cladding process of the method for the invention self assembly can uniformly will be more
The TiO in hole2Coating is on positive electrode grain surface, due to the improvement of the method for cladding, so last lithium ion battery
Chemical property is also just more superior, and commercial value is bigger.
Brief description of the drawings
Fig. 1 is the XRD for the MOFs (MIL-125@Ti) that the embodiment of the present invention 1 is synthesized；
Fig. 2 is the TiO obtained after the MOFs (MIL-125@Ti) that the embodiment of the present invention 1 is synthesized is sintered2XRD；
Fig. 3 is the first discharge specific capacity figure of the embodiment of the present invention 1 ~ 10.
Embodiment
The present invention is further illustrated with reference to specific embodiment, it should be pointed out that following examples are served only for
Bright specific implementation method of the invention, can not limit rights protection scope of the present invention.
Embodiment 1
The method of anode material for lithium-ion batteries coating modification, specifically includes following steps described in the present embodiment：
(1) at room temperature, it is 1 according to mol ratio by butyl titanate, terephthalic acid (TPA), methanol and dimethylformamide：2：15：60
It is made into mixed solution；Again by positive electrode LiNi0.5Co0.2Mn0.3O2Pour into solution mixed above, and with mechanical agitation and
The ultrasonic vibration sufficiently long time, make medicine therein and positive electrode LiNi0.5Co0.2Mn0.3O2It is well mixed, wherein positive pole
Material LiNi0.5Co0.2Mn0.3O2Mol ratio with butyl titanate is 100：0.5.
(2) solution being well mixed in (1) is transferred to the high pressure that temperature has been raised to 120 DEG C of polytetrafluoroethyllining lining
In reactor, and kept for 12 hours, reaction obtains initial positive electrode LiNi0.5Co0.2Mn0.3O2With MOFs (MIL-125@
Ti mixture).
(3) (2) reaction is obtained into turbid liquid and carries out suction filtration, then by obtained filter cake more than 80 DEG C, be dried in vacuo whole night, most
Desciccate is ground using agate mortar afterwards, until crossing the sieve of 300 mesh.
(4) by the powder in (3) by grinding, in atmosphere with 380 DEG C of 4 hours of calcining, that is, obtain finally coating
Positive electrode.
XRD picture such as Fig. 1 of MOFs (MIL-125@Ti) obtained by the present embodiment step (2), it can be seen that synthesized
Product really be porous metal-organic framework materials；By Fig. 2, i.e. the present embodiment step (2) synthesis MOFs (MIL-125@
Ti) product TiO resulting after oversintering2, it can be seen that the TiO obtained by under this sintering temperature2For Rutile Type and
The mixture of Anatase；By the positive electrode of coating modification, by EDS detections it can be seen that titanium elements are in positive electrode
Well mixed, this plays conclusive effect to improve the chemical property of positive electrode；After coating as seen from Figure 3 just
Pole material first discharge specific capacity is 156.48mAhg-1, it is 83.69% that 50 capability retentions are circulated under 1C multiplying power.
Embodiment 2
(1) at room temperature, it is according to mol ratio by tetrabutyl titanate, formic acid, diaminourea terephthalic acid (TPA) and dimethylformamide
1：1.5：20：60 are made into mixed solution；Again by positive electrode LiNi0.5Co0.2Mn0.3O2Pour into solution mixed above, and it is adjoint
Mechanical agitation and ultrasonic vibration sufficiently long time, make medicine therein and positive electrode LiNi0.5Co0.2Mn0.3O2Mixing is equal
It is even, wherein positive electrode LiNi0.5Co0.2Mn0.3O2Mol ratio with tetrabutyl titanate is 100：1.
(2) solution being well mixed in (1) is transferred to the high pressure that temperature has been raised to 120 DEG C of polytetrafluoroethyllining lining
In reactor, and kept for 24 hours, reaction obtains initial positive electrode LiNi0.5Co0.2Mn0.3O2With MOFs (MIL-125-
NH2@Ti) mixture.
(3) (2) reaction is obtained into turbid liquid and carries out suction filtration, then by obtained filter cake more than 80 DEG C, be dried in vacuo whole night, most
Desciccate is ground using agate mortar afterwards, until crossing the sieve of 300 mesh.
(4) by the powder in (3) by grinding, in atmosphere with 480 DEG C of 2 hours of calcining, that is, obtain finally coating
Positive electrode.
The positive electrode after coating modification obtained by the present embodiment step (4), after coating as seen from Figure 3 just
Pole material first discharge specific capacity is 164.37mAhg-1, it is 87.52% that 50 capability retentions are circulated under 1C multiplying power.
Embodiment 3
(1) at room temperature, it is 1 according to mol ratio by titanium tetraisopropylate, P123, terephthalic acid (TPA) and dimethylformamide：1.5：
25：60 are made into mixed solution；Again by positive electrode LiNi0.5Co0.2Mn0.3O2Pour into solution mixed above, and stirred with machinery
The ultrasonic vibration sufficiently long time is mixed and stirred, makes medicine therein and positive electrode LiNi0.5Co0.2Mn0.3O2It is well mixed, wherein
Positive electrode LiNi0.5Co0.2Mn0.3O2Mol ratio with isopropyl titanate is 100：1.
(2) solution being well mixed in (1) is transferred to the high pressure that temperature has been raised to 120 DEG C of polytetrafluoroethyllining lining
In reactor, and kept for 36 hours, reaction obtains initial positive electrode LiNi0.5Co0.2Mn0.3O2With MOFs (MIL-125@
Ti mixture).
(3) (2) reaction is obtained into turbid liquid and carries out suction filtration, then by obtained filter cake more than 80 DEG C, be dried in vacuo whole night, most
Desciccate is ground using agate mortar afterwards, until crossing the sieve of 300 mesh.
(4) by the powder in (3) by grinding, in atmosphere with 580 DEG C of 2 hours of calcining, that is, obtain finally coating
Positive electrode.
The positive electrode after coating modification obtained by the present embodiment step (4), the positive pole after coating as seen from Figure 3
Material first discharge specific capacity is 164.15mAhg-1, it is 90.48% that 50 capability retentions are circulated under 1C multiplying power.
Embodiment 4
(1) at room temperature, it is according to mol ratio by butyl titanate, formic acid, diaminourea terephthalic acid (TPA) and dimethylformamide
1：2.5：30：60 are made into mixed solution；Again by positive electrode LiNi0.5Co0.2Mn0.3O2Pour into solution mixed above, and it is adjoint
Mechanical agitation and ultrasonic vibration sufficiently long time, make medicine therein and positive electrode LiNi0.5Co0.2Mn0.3O2Mixing is equal
It is even, wherein positive electrode LiNi0.5Co0.2Mn0.3O2Mol ratio with isopropyl titanate is 100：1.
(2) solution being well mixed in (1) is transferred to the high pressure that temperature has been raised to 200 DEG C of polytetrafluoroethyllining lining
In reactor, and kept for 18 hours, reaction obtains initial positive electrode LiNi0.5Co0.2Mn0.3O2With MOFs (MIL-125-
NH2@Ti) mixture.
(3) (2) reaction is obtained into turbid liquid and carries out suction filtration, then by obtained filter cake more than 80 DEG C, be dried in vacuo whole night, most
Desciccate is ground using agate mortar afterwards, until crossing the sieve of 300 mesh.
(4) by the powder in (3) by grinding, in atmosphere with 580 DEG C of 6 hours of calcining, that is, obtain finally coating
Positive electrode.
The positive electrode after coating modification obtained by the present embodiment step (4), the positive pole after coating as seen from Figure 3
Material first discharge specific capacity is 163.91mAhg-1, it is 85.37% that 50 capability retentions are circulated under 1C multiplying power.
Embodiment 5
(1) at room temperature, it is 1 according to mol ratio by butyl titanate, methanol, terephthalic acid (TPA) and dimethylformamide：3：15：50
It is made into mixed solution；Again by positive electrode LiNi0.5Co0.2Mn0.3O2Pour into solution mixed above, and with mechanical agitation and
The ultrasonic vibration sufficiently long time, make medicine therein and positive electrode LiNi0.5Co0.2Mn0.3O2It is well mixed, wherein positive pole
Material LiNi0.5Co0.2Mn0.3O2Mol ratio with butyl titanate is 100：2.
(2) solution being well mixed in (1) is transferred to the high pressure that temperature has been raised to 180 DEG C of polytetrafluoroethyllining lining
In reactor, and kept for 12 hours, reaction obtains initial positive electrode LiNi0.5Co0.2Mn0.3O2With MOFs (MIL-125@
Ti mixture).
(3) (2) reaction is obtained into turbid liquid and carries out suction filtration, then by obtained filter cake more than 80 DEG C, be dried in vacuo whole night, most
Desciccate is ground using agate mortar afterwards, until crossing the sieve of 300 mesh.
(4) by the powder in (3) by grinding, in atmosphere with 200 DEG C of 12 hours of calcining, that is, obtain finally coating
Positive electrode.
The positive electrode after coating modification obtained by the present embodiment step (4), the positive pole after coating as seen from Figure 3
Material first discharge specific capacity is 164.52mAhg-1, it is 88.68% that 50 capability retentions are circulated under 1C multiplying power.
Embodiment 6
(1) at room temperature, it is according to mol ratio by tetrabutyl titanate, formic acid, diaminourea terephthalic acid (TPA) and dimethylformamide
1：1.5：15：40 are made into mixed solution；Again by positive electrode LiNi0.5Co0.2Mn0.3O2Pour into solution mixed above, and it is adjoint
Mechanical agitation and ultrasonic vibration sufficiently long time, make medicine therein and positive electrode LiNi0.5Co0.2Mn0.3O2Mixing is equal
It is even, wherein positive electrode LiNi0.5Co0.2Mn0.3O2Mol ratio with tetrabutyl titanate is 100：3.
(2) solution being well mixed in (1) is transferred to the high pressure that temperature has been raised to 150 DEG C of polytetrafluoroethyllining lining
In reactor, and kept for 30 hours, reaction obtains initial positive electrode LiNi0.5Co0.2Mn0.3O2With MOFs (MIL-125-
NH2@Ti) mixture.
(3) (2) reaction is obtained into turbid liquid and carries out suction filtration, then by obtained filter cake more than 80 DEG C, be dried in vacuo whole night, most
Desciccate is ground using agate mortar afterwards, until crossing the sieve of 300 mesh.
(4) by the powder in (3) by grinding, in atmosphere with 580 DEG C of 6 hours of calcining, that is, obtain finally coating
Positive electrode.
The positive electrode after coating modification obtained by the present embodiment step (4), the positive pole after coating as seen from Figure 3
Material first discharge specific capacity is 163.71mAhg-1, it is 89.12% that 50 capability retentions are circulated under 1C multiplying power.
Embodiment 7
(1) at room temperature, it is 1 according to mol ratio by isopropyl titanate, methanol, terephthalic acid (TPA) and dimethylformamide：1.5：
20：60 are made into mixed solution；Again by positive electrode LiNi0.5Co0.2Mn0.3O2Pour into solution mixed above, and stirred with machinery
The ultrasonic vibration sufficiently long time is mixed and stirred, makes medicine therein and positive electrode LiNi0.5Co0.2Mn0.3O2It is well mixed, wherein
Positive electrode LiNi0.5Co0.2Mn0.3O2Mol ratio with isopropyl titanate is 100：2.
(2) solution being well mixed in (1) is transferred to the high pressure that temperature has been raised to 180 DEG C of polytetrafluoroethyllining lining
In reactor, and kept for 12 hours, reaction obtains initial positive electrode LiNi0.5Co0.2Mn0.3O2With MOFs (MIL-125@
Ti mixture).
(3) (2) reaction is obtained into turbid liquid and carries out suction filtration, then by obtained filter cake more than 80 DEG C, be dried in vacuo whole night, most
Desciccate is ground using agate mortar afterwards, until crossing the sieve of 300 mesh.
(4) by the powder in (3) by grinding, in atmosphere with 380 DEG C of 8 hours of calcining, that is, obtain finally coating
Positive electrode.
The positive electrode after coating modification obtained by the present embodiment step (4), the positive pole after coating as seen from Figure 3
Material first discharge specific capacity is 159.59mAhg-1, it is 83.54% that 50 capability retentions are circulated under 1C multiplying power.
Embodiment 8
(1) at room temperature, it is according to mol ratio by butyl titanate, P123, diaminourea terephthalic acid (TPA) and dimethylformamide
1：2.5：25：60 are made into mixed solution；Again by positive electrode LiNi0.5Co0.2Mn0.3O2Pour into solution mixed above, and it is adjoint
Mechanical agitation and ultrasonic vibration sufficiently long time, make medicine therein and positive electrode LiNi0.5Co0.2Mn0.3O2Mixing is equal
It is even, wherein positive electrode LiNi0.5Co0.2Mn0.3O2Mol ratio with butyl titanate is 100：3.
(2) solution being well mixed in (1) is transferred to the high pressure that temperature has been raised to 120 DEG C of polytetrafluoroethyllining lining
In reactor, and kept for 36 hours, reaction obtains initial positive electrode LiNi0.5Co0.2Mn0.3O2With MOFs (MIL-125-
NH2@Ti) mixture.
(3) (2) reaction is obtained into turbid liquid and carries out suction filtration, then by obtained filter cake more than 80 DEG C, be dried in vacuo whole night, most
Desciccate is ground using agate mortar afterwards, until crossing the sieve of 300 mesh.
(4) by the powder in (3) by grinding, in atmosphere with 580 DEG C of 10 hours of calcining, i.e., finally coated
Good positive electrode.
The positive electrode after coating modification obtained by the present embodiment step (4), the positive pole after coating as seen from Figure 3
Material first discharge specific capacity is 166.82mAhg-1, it is 85.71% that 50 capability retentions are circulated under 1C multiplying power.
Embodiment 9
(1) at room temperature, it is 1 according to mol ratio by isopropyl titanate, methanol, terephthalic acid (TPA) and dimethylformamide：2.5：30：
60 are made into mixed solution；Again by positive electrode LiNi0.5Co0.2Mn0.3O2Pour into solution mixed above, and with mechanical agitation
With the ultrasonic vibration sufficiently long time, make medicine therein and positive electrode LiNi0.5Co0.2Mn0.3O2It is well mixed, wherein just
Pole material LiNi0.5Co0.2Mn0.3O2Mol ratio with isopropyl titanate is 100：0.5.
(2) solution being well mixed in (1) is transferred to the high pressure that temperature has been raised to 200 DEG C of polytetrafluoroethyllining lining
In reactor, and kept for 36 hours, reaction obtains initial positive electrode LiNi0.5Co0.2Mn0.3O2With MOFs (MIL-125@
Ti mixture).
(3) (2) reaction is obtained into turbid liquid and carries out suction filtration, then by obtained filter cake more than 80 DEG C, be dried in vacuo whole night, most
Desciccate is ground using agate mortar afterwards, until crossing the sieve of 300 mesh.
(4) by the powder in (3) by grinding, in atmosphere with 380 DEG C of 6 hours of calcining, that is, obtain finally coating
Positive electrode.
The positive electrode after coating modification obtained by the present embodiment step (4), the positive pole after coating as seen from Figure 3
Material first discharge specific capacity is 155.28mAhg-1, it is 86.83% that 50 capability retentions are circulated under 1C multiplying power.
Embodiment 10
(1) at room temperature, it is 1 according to mol ratio by butyl titanate, methanol, terephthalic acid (TPA) and dimethylformamide：2：15：60
It is made into mixed solution；Again by positive electrode LiNi0.5Co0.2Mn0.3O2Pour into solution mixed above, and with mechanical agitation and
The ultrasonic vibration sufficiently long time, make medicine therein and positive electrode LiNi0.5Co0.2Mn0.3O2It is well mixed, wherein positive pole
Material LiNi0.5Co0.2Mn0.3O2Mol ratio with butyl titanate is 100：0.
(2) solution being well mixed in (1) is transferred to the height that temperature has been raised to 120 DEG C of polytetrafluoroethyllining lining
Press in reactor, and kept for 12 hours, reaction obtains initial positive electrode LiNi0.5Co0.2Mn0.3O2With MOFs (MIL-
125@Ti) mixture.
(3) (2) reaction is obtained into turbid liquid and carries out suction filtration, then by obtained filter cake more than 80 DEG C, be dried in vacuo whole night, most
Desciccate is ground using agate mortar afterwards, until crossing the sieve of 300 mesh.
(4) by the powder in (3) by grinding, in atmosphere with 380 DEG C of 4 hours of calcining, that is, obtain finally coating
Positive electrode.
Positive electrode obtained by the present embodiment step (4), as seen from Figure 3 its first discharge specific capacity be
167.72mAhg-1, although and the positive electrode by cladding processing is almost, but cycle performance and high rate performance are all poor.
Embodiment 11
(1) at room temperature, it is according to mol ratio by tetrabutyl titanate, formic acid, diaminourea terephthalic acid (TPA) and dimethylformamide
1：1.5：20：60 are made into mixed solution；Again by positive electrode LiCoO2Pour into solution mixed above, and with mechanical agitation and
The ultrasonic vibration sufficiently long time, make medicine therein and positive electrode LiCoO2It is well mixed, wherein positive electrode LiCoO2With
The mol ratio of tetrabutyl titanate is 100：1.
(2) solution being well mixed in (1) is transferred to the high pressure that temperature has been raised to 120 DEG C of polytetrafluoroethyllining lining
In reactor, and kept for 24 hours, reaction obtains initial positive electrode LiCoO2With MOFs (MIL-125-NH2@Ti) it is mixed
Compound.
(3) (2) reaction is obtained into turbid liquid and carries out suction filtration, then by obtained filter cake more than 80 DEG C, be dried in vacuo whole night, most
Desciccate is ground using agate mortar afterwards, until crossing the sieve of 300 mesh.
(4) by the powder in (3) by grinding, in atmosphere with 480 DEG C of 2 hours of calcining, that is, obtain finally coating
Positive electrode.
The positive electrode first discharge specific capacity after coating modification obtained by the present embodiment step (4) is
172.71mAhg-1；It is 93.23% that 50 capability retentions are circulated under 1C multiplying power.
Embodiment 12
(1) at room temperature, it is 1 according to mol ratio by isopropyl titanate, methanol, terephthalic acid (TPA) and dimethylformamide：1.5：
25：60 are made into mixed solution；Again by positive electrode LiNiO2Pour into solution mixed above, and shaken with mechanical agitation and ultrasound
The sufficiently long time is moved, makes medicine therein and positive electrode LiNiO2It is well mixed, wherein positive electrode LiNiO2It is different with metatitanic acid
The mol ratio of propyl ester is 100：1.
(2) solution being well mixed in (1) is transferred to the high pressure that temperature has been raised to 120 DEG C of polytetrafluoroethyllining lining
In reactor, and kept for 36 hours, reaction obtains initial positive electrode LiNiO2With MOFs (MIL-125@Ti) mixing
Thing.
(3) (2) reaction is obtained into turbid liquid and carries out suction filtration, then by obtained filter cake more than 80 DEG C, be dried in vacuo whole night, most
Desciccate is ground using agate mortar afterwards, until crossing the sieve of 300 mesh.
(4) by the powder in (3) by grinding, in atmosphere with 580 DEG C of 2 hours of calcining, that is, obtain finally coating
Positive electrode.
The positive electrode first discharge specific capacity after coating modification obtained by the present embodiment step (4) is
183.59mAhg-1；It is 85.74% that 50 capability retentions are circulated under 1C multiplying power.
Embodiment 13
(1) at room temperature, it is according to mol ratio by butyl titanate, formic acid, diaminourea terephthalic acid (TPA) and dimethylformamide
1：2.5：30：60 are made into mixed solution；Again by positive electrode LiMnO2Pour into solution mixed above, and with mechanical agitation and
The ultrasonic vibration sufficiently long time, make medicine therein and positive electrode LiMnO2It is well mixed, wherein positive electrode LiMnO2With
The mol ratio of isopropyl titanate is 100：1.
(2) solution being well mixed in (1) is transferred to the high pressure that temperature has been raised to 200 DEG C of polytetrafluoroethyllining lining
In reactor, and kept for 18 hours, reaction obtains initial anode material LiMnO2With MOFs (MIL-125-NH2@Ti) mixing
Thing.
(3) (2) reaction is obtained into turbid liquid and carries out suction filtration, then by obtained filter cake more than 80 DEG C, be dried in vacuo whole night, most
Desciccate is ground using agate mortar afterwards, until crossing the sieve of 300 mesh.
(4) by the powder in (3) by grinding, in atmosphere with 580 DEG C of 6 hours of calcining, that is, obtain finally coating
Positive electrode.
The positive electrode first discharge specific capacity after coating modification obtained by the present embodiment step (4) is
187.64mAhg-1；It is 96.11% that 50 capability retentions are circulated under 1C multiplying power.
Embodiment 14
(1) at room temperature, it is 1 according to mol ratio by butyl titanate, methanol, terephthalic acid (TPA) and dimethylformamide：3：15：50
It is made into mixed solution；Again by positive electrode LiNi0.8Co0.2O2Pour into solution mixed above, and with mechanical agitation and ultrasound
The sufficiently long time is vibrated, makes medicine therein and positive electrode LiNi0.8Co0.2O2It is well mixed, wherein positive electrode
LiNi0.8Co0.2O2Mol ratio with butyl titanate is 100：2.
(2) solution being well mixed in (1) is transferred to the high pressure that temperature has been raised to 180 DEG C of polytetrafluoroethyllining lining
In reactor, and kept for 12 hours, reaction obtains initial positive electrode LiNi0.8Co0.2O2With MOFs (MIL-125@Ti)
Mixture.
(3) (2) reaction is obtained into turbid liquid and carries out suction filtration, then by obtained filter cake more than 80 DEG C, be dried in vacuo whole night, most
Desciccate is ground using agate mortar afterwards, until crossing the sieve of 300 mesh.
(4) by the powder in (3) by grinding, in atmosphere with 200 DEG C of 12 hours of calcining, that is, obtain finally coating
Positive electrode.
The positive electrode first discharge specific capacity after coating modification obtained by the present embodiment step (4) is
190.58mAhg-1；It is 94.36% that 50 capability retentions are circulated under 1C multiplying power.
Embodiment 15
(1) at room temperature, it is according to mol ratio by tetrabutyl titanate, formic acid, diaminourea terephthalic acid (TPA) and dimethylformamide
1：1.5：15：40 are made into mixed solution；Again by positive electrode LiNi0.5Mn0.5O2Pour into solution mixed above, and with machinery
Stirring and ultrasonic vibration sufficiently long time, make medicine therein and positive electrode LiNi0.5Mn0.5O2It is well mixed, wherein just
Pole material LiNi0.5Mn0.5O2Mol ratio with tetrabutyl titanate is 100：3.
(2) solution being well mixed in (1) is transferred to the high pressure that temperature has been raised to 150 DEG C of polytetrafluoroethyllining lining
In reactor, and kept for 30 hours, reaction obtains initial positive electrode LiNi0.5Mn0.5O2With MOFs (MIL-125-NH2@
Ti mixture).
(3) (2) reaction is obtained into turbid liquid and carries out suction filtration, then by obtained filter cake more than 80 DEG C, be dried in vacuo whole night, most
Desciccate is ground using agate mortar afterwards, until crossing the sieve of 300 mesh.
(4) by the powder in (3) by grinding, in atmosphere with 580 DEG C of 6 hours of calcining, that is, obtain finally coating
Positive electrode.
The positive electrode first discharge specific capacity after coating modification obtained by the present embodiment step (4) is
178.27mAhg-1；It is 86.46% that 50 capability retentions are circulated under 1C multiplying power.
Embodiment 16
(1) at room temperature, it is 1 according to mol ratio by isopropyl titanate, methanol, terephthalic acid (TPA) and dimethylformamide：1.5：
20：60 are made into mixed solution；Again by positive electrode LiFePO4Pour into solution mixed above, and with mechanical agitation and ultrasound
The sufficiently long time is vibrated, makes medicine therein and positive electrode LiFePO4It is well mixed, wherein positive electrode LiFePO4With titanium
The mol ratio of isopropyl propionate is 100：2.
(2) solution being well mixed in (1) is transferred to the high pressure that temperature has been raised to 180 DEG C of polytetrafluoroethyllining lining
In reactor, and kept for 12 hours, reaction obtains initial positive electrode LiFePO4With MOFs (MIL-125@Ti) mixing
Thing.
(3) (2) reaction is obtained into turbid liquid and carries out suction filtration, then by obtained filter cake more than 80 DEG C, be dried in vacuo whole night, most
Desciccate is ground using agate mortar afterwards, until crossing the sieve of 300 mesh.
(4) by the powder in (3) by grinding, in atmosphere with 380 DEG C of 8 hours of calcining, that is, obtain finally coating
Positive electrode.
The positive electrode first discharge specific capacity after coating modification obtained by the present embodiment step (4) is
108.27mAhg-1；It is 96.83% that 50 capability retentions are circulated under 1C multiplying power.
Claims (6)
1. a kind of method of anode material for lithium-ion batteries coating modification, it is characterised in that specifically include following steps：
(1) at room temperature, it is 1 according to mol ratio by organic titanium salt, part, template and organic solvent：(1.5~3)：(15~
30)：The ratio of (40 ~ 60) is made into mixed solution, then anode material for lithium-ion batteries is added in mixed solution, makes lithium-ion electric
Pond positive electrode is well mixed with mixed solution obtains mixture；Wherein, anode material for lithium-ion batteries and organic titanium salt rub
You are than being 100：(0.5~3.0)；
(2) mixture for obtaining step (1) is added and is transferred in autoclave, and 12 are reacted at a temperature of 120 ~ 200 DEG C
~36 h；
(3) the turbid liquid after the completion of being reacted in step (2) is subjected to suction filtration, 300 mesh sieves, grinding is crossed after filter cake vacuum drying, grinding
Powder afterwards, calcines 2~12 hours at a temperature of 200~580 DEG C, that is, obtains the lithium ion cell positive finally coated
Material.
2. the method for anode material for lithium-ion batteries coating modification according to claim 1, it is characterised in that：In step (1)
The template is methanol, formic acid or P123。
3. the method for anode material for lithium-ion batteries coating modification according to claim 1, it is characterised in that：In step (1)
The organic solvent is dimethylformamide.
4. the method for anode material for lithium-ion batteries coating modification according to claim 1, it is characterised in that in step (1)
The part is terephthalic acid (TPA) or diaminourea terephthalic acid (TPA).
5. the method for anode material for lithium-ion batteries coating modification according to claim 1, it is characterised in that step (1) institute
Organic titanium salt is stated for tetrabutyl titanate, butyl titanate, butyl titanate, isopropyl titanate, isopropyl titanate or titanium tetraisopropylate.
6. the method for anode material for lithium-ion batteries coating modification according to claim 1, it is characterised in that：Lithium ion battery
Positive electrode is ternary nickel cobalt manganese anode material for lithium-ion batteries LiNi x Co y Mn z O2, wherein 0≤x≤1,0≤y≤1,0≤z≤
1, x+y+z=1.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103855387A (en) * | 2014-03-25 | 2014-06-11 | 海宁美达瑞新材料科技有限公司 | Modified lithium ion battery ternary positive electrode material and preparation method thereof |
| CN104716309A (en) * | 2015-02-11 | 2015-06-17 | 江苏科捷锂电池有限公司 | Preparation method of high-voltage ternary anode material wrapped with TiO2 in sectional mode |
| CN106099047A (en) * | 2016-08-25 | 2016-11-09 | 深圳市贝特瑞纳米科技有限公司 | A kind of surface coating method of electrode material and application thereof |
-
2017
- 2017-04-21 CN CN201710265912.5A patent/CN107195899A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103855387A (en) * | 2014-03-25 | 2014-06-11 | 海宁美达瑞新材料科技有限公司 | Modified lithium ion battery ternary positive electrode material and preparation method thereof |
| CN104716309A (en) * | 2015-02-11 | 2015-06-17 | 江苏科捷锂电池有限公司 | Preparation method of high-voltage ternary anode material wrapped with TiO2 in sectional mode |
| CN106099047A (en) * | 2016-08-25 | 2016-11-09 | 深圳市贝特瑞纳米科技有限公司 | A kind of surface coating method of electrode material and application thereof |
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| CN108390022A (en) * | 2017-12-29 | 2018-08-10 | 桑德集团有限公司 | Lithium battery tertiary cathode material, preparation method and the lithium battery of carbon-metal oxide compound coating |
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| CN109411735A (en) * | 2018-11-30 | 2019-03-01 | 厦门大学 | A kind of positive electrode and preparation method thereof and lithium ion battery |
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Application publication date: 20170922 |