CN106058192B - A kind of coating modification layered cathode material of lithium ion battery and preparation method thereof - Google Patents
A kind of coating modification layered cathode material of lithium ion battery and preparation method thereof Download PDFInfo
- Publication number
- CN106058192B CN106058192B CN201610572497.3A CN201610572497A CN106058192B CN 106058192 B CN106058192 B CN 106058192B CN 201610572497 A CN201610572497 A CN 201610572497A CN 106058192 B CN106058192 B CN 106058192B
- Authority
- CN
- China
- Prior art keywords
- vdf
- cathode material
- lithium ion
- ion battery
- layered cathode
- 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.)
- Active
Links
- 239000010406 cathode material Substances 0.000 title claims abstract description 44
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 38
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 239000011248 coating agent Substances 0.000 title claims abstract description 20
- 238000000576 coating method Methods 0.000 title claims abstract description 20
- 230000004048 modification Effects 0.000 title claims abstract description 18
- 238000012986 modification Methods 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 238000005253 cladding Methods 0.000 claims abstract description 24
- 238000003756 stirring Methods 0.000 claims abstract description 24
- 238000001035 drying Methods 0.000 claims abstract description 19
- 239000000463 material Substances 0.000 claims abstract description 19
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 28
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 27
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 10
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 9
- 229910016722 Ni0.5Co0.2Mn0.3 Inorganic materials 0.000 claims description 5
- 229910016771 Ni0.5Mn0.5 Inorganic materials 0.000 claims description 5
- 229910032387 LiCoO2 Inorganic materials 0.000 claims description 4
- 229910001228 Li[Ni1/3Co1/3Mn1/3]O2 (NCM 111) Inorganic materials 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims 4
- OHLUUHNLEMFGTQ-UHFFFAOYSA-N N-methylacetamide Chemical compound CNC(C)=O OHLUUHNLEMFGTQ-UHFFFAOYSA-N 0.000 claims 2
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 claims 2
- 238000000034 method Methods 0.000 abstract description 11
- 239000011149 active material Substances 0.000 abstract description 2
- 238000009831 deintercalation Methods 0.000 abstract description 2
- 238000005516 engineering process Methods 0.000 abstract description 2
- 238000009830 intercalation Methods 0.000 abstract description 2
- 230000002687 intercalation Effects 0.000 abstract description 2
- 230000035800 maturation Effects 0.000 abstract 1
- 229920006254 polymer film Polymers 0.000 abstract 1
- 239000011572 manganese Substances 0.000 description 21
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 21
- 239000002033 PVDF binder Substances 0.000 description 11
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 11
- 206010013786 Dry skin Diseases 0.000 description 8
- 239000004642 Polyimide Substances 0.000 description 6
- 229920001721 polyimide Polymers 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 5
- 230000008901 benefit Effects 0.000 description 5
- 229940113088 dimethylacetamide Drugs 0.000 description 5
- 239000010410 layer Substances 0.000 description 5
- 239000002322 conducting polymer Substances 0.000 description 4
- 229920001940 conductive polymer Polymers 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- MIZLGWKEZAPEFJ-UHFFFAOYSA-N 1,1,2-trifluoroethene Chemical group FC=C(F)F MIZLGWKEZAPEFJ-UHFFFAOYSA-N 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical compound FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 3
- 239000010405 anode material Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 150000004040 pyrrolidinones Chemical class 0.000 description 2
- QTHKJEYUQSLYTH-UHFFFAOYSA-N [Co]=O.[Ni].[Li] Chemical compound [Co]=O.[Ni].[Li] QTHKJEYUQSLYTH-UHFFFAOYSA-N 0.000 description 1
- 238000004026 adhesive bonding Methods 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000008429 bread Nutrition 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000004087 circulation Effects 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000005621 ferroelectricity Effects 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 1
- VGYDTVNNDKLMHX-UHFFFAOYSA-N lithium;manganese;nickel;oxocobalt Chemical compound [Li].[Mn].[Ni].[Co]=O VGYDTVNNDKLMHX-UHFFFAOYSA-N 0.000 description 1
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 1
- CPABIEPZXNOLSD-UHFFFAOYSA-N lithium;oxomanganese Chemical compound [Li].[Mn]=O CPABIEPZXNOLSD-UHFFFAOYSA-N 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229920005575 poly(amic acid) Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000005616 pyroelectricity Effects 0.000 description 1
- 230000003252 repetitive effect Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 239000002345 surface coating layer Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 229910052725 zinc 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
-
- 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
-
- 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
- H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
- H01M4/602—Polymers
-
- 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)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
It is to coat P (VDF-TFE) or P (VDF-TrFE) film on layered cathode material of lithium ion battery surface the invention discloses a kind of coating modification layered cathode material of lithium ion battery；The invention also discloses preparation methods, comprise the concrete steps that: 1) firstly, take a certain amount of P (VDF-TFE) or P (VDF-TrFE) be added in organic solution, stirring and dissolving；2) in the solution after layered cathode material of lithium ion battery to be added to above-mentioned stirring and dissolving, after mixing evenly, the presoma after 60 ~ 110 DEG C are dried to obtain cladding；3) persursor material after drying is placed in tube furnace, is heated 2 ~ 5h at a temperature of 100 ~ 150 DEG C under air or vacuum condition, obtain surface cladding 0.5wt% ~ 5wt%P (VDF-TFE) or the target product of P (VDF-TrFE)；The clad is conducive to raising and the Li of the conductivity of layered cathode material+In active material intercalation/deintercalation and after coating positive electrode surface polymer film layer uniformity, continuity it is good, while this method technology maturation is reliable.
Description
Technical field
The invention belongs to the preparation field of layered cathode material of lithium ion battery, especially a kind of coating modification lithium-ion electric
Pond layered cathode material and preparation method thereof.
Background technique
Since lithium ion battery has, energy density is high, light-weight, memory-less effect, good rate capability, has extended cycle life
Etc. a series of advantage, wherein this high outstanding advantages of energy density make lithium ion battery be acknowledged as a new generation electronic
The ideal power energy of automobile, mixed power electric car.Wherein, the energy density of lithium ion battery depends primarily on positive material
The energy density of material；The energy density of positive electrode is high, and the energy density of lithium ion battery is inevitable also high.Therefore, high energy is developed
The positive electrode of metric density becomes the focus of people's research.In numerous lithium ion anode materials, layered cathode material has height
It the advantages that theoretical capacity, high ionic mobility, is even more pursued by people.
In lithium ion battery, side reaction, metallic element in the positive electrode after corrosion occur for positive electrode and electrolyte
The problems such as dissolving the increase of (such as Mn), solid electrolyte interface film, so as to cause the capacity attenuation of battery, and leads to cycle performance
Decline；In addition, mean voltage decline caused by material phase structure changes is also one of strategic point problem to be solved.Therefore, it is necessary to adopt
The chemical property of layered cathode material of lithium ion battery is improved with surface coated technological means.Cladding mode now is big
Body can be divided into two kinds: dry method cladding and wet process coat.For opposite dry method cladding, wet process is evenly coated, and obtained anode
The chemical property of material is more superior.By taking Chinese patent application as an example (publication number: CN200310112600.9), wet process is used
Improve cycle performance, the height of material in lithium cobalt oxide, lithium-nickel-cobalt-oxygen, lithium nickel cobalt manganese oxygen, lithium manganese-oxygen material oxide coated on surface
Temperature stability, high rate performance and security performance, wherein oxide be metal Al, Mg, Zn, Ca, Ba, Ti, V, Sn or nonmetallic Si,
The oxide of a certain element in B.Traditional wet process cladding is mainly sol-gel method, however, this method is there are wretched insufficiency,
Such as surface coating layer uneven thickness, and coating thickness can not controllable precise or even some regions clad occur imperfect.This
A little deficiencies will directly affect the chemical property of positive electrode.Wang Jiulin seminar, Shanghai Communications University is in ACS Applied
It has been delivered on Materials and Interfaces magazine and Li is coated with polyamic acid (PAA)1.2[Mn0.54Ni0.13Co0.13]
O2, then obtain polyimides (PI) through the high temperature anneal and coat Li1.2[Mn0.54Ni0.13Co0.13]O2(Polyimide
Encapsulated Lithium-Rich Cathode Material for HighVoltage Lithium-Ion
Battery 2014,6,17965 is 17973).PAA has highly polar, excellent filming performance, has with transition metal oxide
Stronger affinity is conducive to it in active electrode surface and forms continuous PI ion conductive layer.Therefore, the anode after PI is coated
Material shows excellent chemical property.But even across 450 DEG C of high annealings after, PAA also fails to be completely converted into
PI。
Conducting polymer be by have altogether grip π-key macromolecule through chemistry or electrochemistry " doping " make its by insulator turn
Become a kind of macromolecule polymer material of conductor.Conducting polymer not only conductivity with higher the advantages of, but also have
The good characteristics such as photoconductive property, nonlinear optical property, luminous and magnetic property, and conducting polymer flexibility is good, production
At low cost, efficiency is high.Kynoar (PVDF) is organic piezoelectric materials, also known as piezopolymer, has material flexible, low close
The advantages that degree, Low ESR, high conductance and high pressure piezoelectric voltage constant, during assembled battery, PVDF is often used as gluing
Connect agent use.The repetitive unit of PVDF chemical formula is-CH2–CF2, it is very high that simple linear structure has PVDF strand
Flexibility.Meanwhile the vertical structure limitation that stronger dipole-dipole interaction generates between C-F key, so that PVDF has a variety of crystallizations
Form.The arrangement mode of molecule is different in PVDF, and polarity can be also varied.In five kinds of crystal forms being currently known, β phase
PVDF molecular polarity it is maximum, structure is in alltrans conformation.Polar beta phase PVDF's has good ferroelectricity, piezoelectricity, pyroelectricity
Characteristic, however the thermodynamically stable phase and non-beta phase of PVDF crystallization, but nonpolar α phase.Research has shown that, is added in PVDF
Tetrafluoroethene (TFE) or trifluoro-ethylene (TrFE), the bipolymer P (VDF-TFE) and P (VDF-TrFE) that can make
Alltrans conformation (β phase) it is lower than the energy of trans--Ponds conformation (α phase), therefore it is β that this kind of bipolymer, which is easier to crystallize,
Phase.Up to the present, bipolymer P (VDF-TFE) and P (VDF-TrFE) coating modification layered cathode material of lithium ion battery
Research have not been reported.
Summary of the invention
The present invention is directed to the deficiencies in the prior art, discloses a kind of coating modification lithium ion battery stratiform anode material
Material and preparation method thereof, can be in the film and the party that layered cathode material of lithium ion battery surface is evenly coated by this method
Law technology mature and reliable.
It is in lithium ion battery stratiform anode the invention discloses a kind of coating modification layered cathode material of lithium ion battery
Material surface coats P (VDF-TFE) or P (VDF-TrFE) film.
The invention also discloses the preparation methods of coating modification layered cathode material of lithium ion battery, the specific steps are as follows:
1) firstly, P (VDF-TFE) is added in organic solution, the wherein mass ratio of P (VDF-TFE) and organic solution
For 1:20 ~ 200, stirring and dissolving；
2) layered cathode material of lithium ion battery is added in above-mentioned solution, after mixing evenly, through 60 ~ 110 DEG C of dryings
Presoma after being coated；
3) persursor material after drying is placed in tube furnace, in air or under vacuum condition, under certain condition
Heated 2 ~ 5h at a temperature of 100 ~ 150 DEG C, obtains the target product of surface cladding 0.5wt% ~ 5wt% P (VDF-TFE).
Further, the organic solution in the step 1) is ethylene carbonate (EC), diethyl carbonate (DEC), N- first
One or more of base pyrrolidones (NMP), dimethyl acetamide (DMAC), dimethylformamide (DMF) mixed solution.
Further, the VDF in the P in the step 1) (VDF-TFE) and TFE molar ratio are 10:90 ~ 90:10.
Further, the layered cathode material in the step 2) includes: unitary layered cathode material LiCoO2；Binary layer
Shape positive electrode Li [Ni0.5Mn0.5]O2；Ternary layered positive electrode Li [Ni1/3Co1/3Mn1/3]O2、Li[Ni0.5Co0.2Mn0.3]
O2、Li[Ni0.6Co0.2Mn0.2]O2、Li1.2[Mn0.51Ni0.19Co0.1]O2、Li1.2[Mn0.54Ni0.13Co0.13]O2。
The invention also discloses the preparation methods of coating modification layered cathode material of lithium ion battery, the specific steps are as follows:
1) firstly, P (VDF-TrFE) is added in organic solution, the wherein mass ratio of P (VDF-TrFE) and organic solution
For 1:20 ~ 200, stirring and dissolving；
2) layered cathode material of lithium ion battery is added in above-mentioned solution, after mixing evenly, through 60 ~ 110 DEG C of dryings
Presoma after being coated；
3) persursor material after drying is placed in tube furnace, in air or under vacuum condition, through 100 ~ 150 DEG C of temperature
Degree is lower to heat 2 ~ 5h, obtains the target product of surface cladding 0.5wt% ~ 5wt% P (VDF-TrFE).
Further, the organic solution in the step 1) is ethylene carbonate (EC), diethyl carbonate (DEC), N- first
One or more of base pyrrolidones (NMP), dimethyl acetamide (DMAC), dimethylformamide (DMF) mixed solution.
Further, the molar ratio of the VDF in the P in the step 1) (VDF-TrFE) and TrFE is 10:90 ~ 90:10.
Further, the layered cathode material in the step 2) includes: unitary layered cathode material LiCoO2；Binary layer
Shape positive electrode Li [Ni0.5Mn0.5]O2；Ternary layered positive electrode Li [Ni1/3Co1/3Mn1/3]O2、Li[Ni0.5Co0.2Mn0.3]
O2、Li[Ni0.6Co0.2Mn0.2]O2、Li1.2[Mn0.51Ni0.19Co0.1]O2、Li1.2[Mn0.54Ni0.13Co0.13]O2。
Compared with prior art, the present invention beneficial effect is:
(1) cycle performance of P (VDF-TFE) and P (VDF-TrFE) film is significantly improved, and even if following in multiple
Higher discharge capacity is still kept after ring.
(2) P (VDF-TFE) and P (VDF-TrFE) film use PVDF base conducting polymer materials, which is conducive to layer
The raising of the conductivity of shape positive electrode and Li+The intercalation/deintercalation in active material；
(3) bipolymer P (VDF-TFE) or P (VDF-TrFE) coating modification lithium ion battery stratiform is used for the first time
Positive electrode, by this method prepare P (VDF-TFE) and P (VDF-TrFE) film is evenly coated and film continuous uniform, centainly
The chemical property of positive electrode is ensured in degree.
Detailed description of the invention
Fig. 1 is 1wt% P (VDF-TrFE) the cladding Li of the embodiment of the present invention 11.2[Mn0.54Ni0.13Co0.13]O2/ Li button
The cycle performance figure of battery.
Fig. 2 is 1wt% P (VDF-TrFE) the cladding Li of the embodiment of the present invention 11.2[Mn0.54Ni0.13Co0.13]O2TEM
Figure.
Specific embodiment
The present invention is specifically described with reference to embodiments.
Embodiment 1
0.1 gram of P (VDF-TrFE) is added in 5 milliliters of DEC solution, stirring and dissolving；Again by 10 grams of layered cathode materials
Li1.2[Mn0.54Ni0.13Co0.13]O2In solution after being added to above-mentioned stirring and dissolving, it is again stirring for uniformly, after 110 DEG C of dryings
Presoma after to cladding；Presoma after drying is placed in tube furnace, is heated in air, through adding at a temperature of 140 DEG C
It is heat-treated 3h, obtains the target product of surface cladding 1wt% P (VDF-TrFE).
As shown in Figure 1, Fig. 1 is 1wt% P (VDF-TrFE) the cladding Li of above-described embodiment 11.2[Mn0.54Ni0.13Co0.13]
O2The cycle performance figure of/Li button cell；Wherein, a Li1.2[Mn0.54Ni0.13Co0.13]O2, b is 1wt% P (VDF-TrFE) packet
Cover Li1.2[Mn0.54Ni0.13Co0.13]O2, Cong Tuzhong passes through 140 DEG C it follows that under identical test condition under vacuum condition
At a temperature of heat 3h P (VDF-TrFE) coat Li1.2[Mn0.54Ni0.13Co0.13]O2The cycle performance of material is significantly mentioned
It rises, and after 100 circulations, capacity retention ratio is up to 90.8%.
As shown in Fig. 2, Fig. 2 is 1wt% P (VDF-TrFE) the cladding Li of above-described embodiment 11.2[Mn0.54Ni0.13Co0.13]
O2TEM figure, Cong Tuzhong is it follows that Li1.2[Mn0.54Ni0.13Co0.13]O2There are one layer of continuous and uniform claddings on surface
Layer, about 5 nanometers of thickness.
Embodiment 2
1 gram of P (VDF-TFE) is added in 10 ml of EC solution, stirring and dissolving；Again by 20 grams of layered cathode material Li
[Ni0.6Co0.2Mn0.2]O2In solution after being added to above-mentioned stirring and dissolving, it is again stirring for uniformly, being coated after 60 DEG C of dryings
Presoma afterwards；Presoma after drying is placed in tube furnace, through heating 3h at a temperature of 140 DEG C under vacuum condition, is obtained
Surface coats the target product of 5wt% P (VDF-TFE).
Embodiment 3
0.1 gram of P (VDF-TrFE) is added in 2 milliliters of nmp solutions, stirring and dissolving；Again by 20 grams of layered cathode materials
Li[Ni0.5Co0.2Mn0.3]O2In solution after being added to above-mentioned stirring and dissolving, it is again stirring for uniformly, being wrapped after 60 DEG C of dryings
Presoma after covering；Presoma after drying is placed in tube furnace, heats 3h at a temperature of in air environment through 140 DEG C,
Obtain the target product of surface cladding 0.5wt% P (VDF-TrFE).
Embodiment 4
0.2 gram of P (VDF-TFE) is added in 5 milliliters of DMF solutions, stirring and dissolving；Again by 20 grams of layered cathode materials
Li1.2[Mn0.51Ni0.19Co0.1]O2In solution after being added to above-mentioned stirring and dissolving, it is again stirring for uniformly, after 100 DEG C of dryings
Presoma after to cladding；Presoma after drying is placed in tube furnace, through heating at a temperature of 110 DEG C under vacuum condition
5h obtains the target product of surface cladding 1wt% P (VDF-TFE).
Embodiment 5
0.2 gram of P (VDF-TrFE) is added in 6 milliliters of DMAC solution, stirring and dissolving；Again by 10 grams of layered cathode materials
Li[Ni0.5Mn0.5]O2In solution after being added to above-mentioned stirring and dissolving, it is again stirring for uniformly, after obtaining cladding after 60 DEG C of dryings
Presoma；Presoma after drying is placed in tube furnace, through heating 2h at a temperature of 150 DEG C under vacuum condition, obtains table
Bread covers the target product of 2wt% P (VDF-TrFE).
Embodiment 6
0.2 gram of P (VDF-TFE) is added in 10 milliliters of DEC solution, stirring and dissolving；Again by 10 grams of layered cathode materials
Li[Ni1/3Ni1/3Mn1/3]O2In solution after being added to above-mentioned stirring and dissolving, it is again stirring for uniformly, being wrapped after 80 DEG C of dryings
Presoma after covering；Presoma after drying is placed in tube furnace, is heated in air, at heating at a temperature of 130 DEG C
5h is managed, the target product of surface cladding 2wt% P (VDF-TFE) is obtained.
There are many concrete application approach of the present invention, the above is only a preferred embodiment of the present invention.It should be pointed out that for
For those skilled in the art, without departing from the principle of the present invention, it can also make several improvements, this
A little improve also should be regarded as protection scope of the present invention.
Claims (8)
1. a kind of preparation method of coating modification layered cathode material of lithium ion battery, which is characterized in that in lithium ion battery layer
Shape positive electrode surface coats P (VDF-TFE) film, the specific steps are as follows:
1) firstly, P (VDF-TFE) is added in organic solution, the mass ratio of P (VDF-TFE) and organic solution be 1:20 ~
200, stirring and dissolving；
2) layered cathode material of lithium ion battery is added in above-mentioned solution, after mixing evenly, is dried to obtain through 60 ~ 110 DEG C
Presoma after cladding；
3) persursor material after drying is placed in tube furnace and is heated, in air or under vacuum environment, through 100 ~ 150
Heat 2 ~ 5h at a temperature of DEG C, obtains the target product of surface cladding 0.5wt% ~ 5wt% P (VDF-TFE).
2. the preparation method of coating modification layered cathode material of lithium ion battery according to claim 1, which is characterized in that institute
Organic solution in the step 1) stated is ethylene carbonate (EC), diethyl carbonate (DEC), N-Methyl pyrrolidone (NMP), two
One or more of methylacetamide (DMAC), dimethylformamide (DMF) mixed solution.
3. the preparation method of coating modification layered cathode material of lithium ion battery according to claim 1, which is characterized in that institute
VDF in P (VDF-TFE) and TFE molar ratio in the step 1) stated are 10:90 ~ 90:10.
4. the preparation method of coating modification layered cathode material of lithium ion battery according to claim 1, which is characterized in that institute
Layered cathode material in the step 2) stated includes: unitary layered cathode material LiCoO2；Binary layered cathode material Li
[Ni0.5Mn0.5]O2；Ternary layered positive electrode Li [Ni1/3Co1/3Mn1/3]O2、Li[Ni0.5Co0.2Mn0.3]O2、Li
[Ni0.6Co0.2Mn0.2]O2、Li1.2[Mn0.51Ni0.19Co0.1]O2、Li1.2[Mn0.54Ni0.13Co0.13]O2One of when.
5. a kind of preparation method of coating modification layered cathode material of lithium ion battery, which is characterized in that in lithium ion battery layer
Shape positive electrode surface coats P (VDF-TrFE) film, the specific steps are as follows:
1) firstly, P (VDF-TrFE) is added in organic solution, the mass ratio of P (VDF-TrFE) and organic solution be 1:20 ~
200, stirring and dissolving；
2) layered cathode material of lithium ion battery is added in above-mentioned solution, after mixing evenly, is dried to obtain through 60 ~ 110 DEG C
Presoma after cladding；
3) persursor material after drying is placed in tube furnace and is heated, in air or under vacuum environment, through 100 ~ 150
Heat 2 ~ 5h at a temperature of DEG C, obtains the target product of surface cladding 0.5wt% ~ 5wt% P (VDF-TrFE).
6. the preparation method of coating modification layered cathode material of lithium ion battery according to claim 5, which is characterized in that institute
Organic solution in the step 1) stated is ethylene carbonate (EC), diethyl carbonate (DEC), N-Methyl pyrrolidone (NMP), two
One or more of methylacetamide (DMAC), dimethylformamide (DMF) mixed solution.
7. the preparation method of coating modification layered cathode material of lithium ion battery according to claim 5, which is characterized in that institute
The molar ratio of the VDF and TrFE in P (VDF-TrFE) in the step 1) stated is 10:90 ~ 90:10.
8. the preparation method of coating modification layered cathode material of lithium ion battery according to claim 5, which is characterized in that institute
Layered cathode material in the step 2) stated includes: unitary layered cathode material LiCoO2；Binary layered cathode material Li
[Ni0.5Mn0.5]O2；Ternary layered positive electrode Li [Ni1/3Co1/3Mn1/3]O2、Li[Ni0.5Co0.2Mn0.3]O2、Li
[Ni0.6Co0.2Mn0.2]O2、Li1.2[Mn0.51Ni0.19Co0.1]O2、Li1.2[Mn0.54Ni0.13Co0.13]O2One of when.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610572497.3A CN106058192B (en) | 2016-07-20 | 2016-07-20 | A kind of coating modification layered cathode material of lithium ion battery and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610572497.3A CN106058192B (en) | 2016-07-20 | 2016-07-20 | A kind of coating modification layered cathode material of lithium ion battery and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106058192A CN106058192A (en) | 2016-10-26 |
| CN106058192B true CN106058192B (en) | 2019-02-26 |
Family
ID=57188115
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610572497.3A Active CN106058192B (en) | 2016-07-20 | 2016-07-20 | A kind of coating modification layered cathode material of lithium ion battery and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106058192B (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106848241A (en) * | 2017-02-27 | 2017-06-13 | 苏州大学 | A kind of preparation method of polymer overmold lithium ion battery electrode material |
| CN107546362A (en) * | 2017-07-17 | 2018-01-05 | 上海工程技术大学 | A kind of electrode with pyroelectric effect and its preparation method and application |
| CN108511744A (en) * | 2018-03-23 | 2018-09-07 | 安普瑞斯（无锡）有限公司 | A kind of anode material for lithium-ion batteries and preparation method thereof that compound coating is modified |
| CN112447959B (en) * | 2020-12-10 | 2022-07-08 | 山东丰元化学股份有限公司 | Surface treatment method of high-nickel ternary cathode material |
| CN112820873B (en) * | 2020-12-31 | 2022-07-05 | 深圳市德方创域新能源科技有限公司 | Polymer-coated lithium battery positive electrode material and preparation method thereof |
| CN113964294B (en) * | 2021-10-28 | 2024-04-12 | 西安交通大学 | Lithium ion battery negative electrode and preparation method and application thereof |
| CN114899399B (en) * | 2022-05-07 | 2023-02-07 | 武汉楚能新能源有限公司 | Carbon coating method of ternary cathode material with PVDF (polyvinylidene fluoride) as carbon source |
| CN114944488B (en) * | 2022-05-23 | 2024-02-09 | 浙江锂威能源科技有限公司 | Preparation method of coated positive electrode material, product and application thereof |
| CN115036500A (en) * | 2022-06-24 | 2022-09-09 | 广东邦普循环科技有限公司 | Cathode material and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102498594A (en) * | 2009-07-25 | 2012-06-13 | 赢创德固赛有限公司 | Coating method for producing electrodes for electrical energy stores |
| CN102569780A (en) * | 2012-02-28 | 2012-07-11 | 南京航空航天大学 | Method for preparing lithium ion battery cathode material with layered structure |
| CN104112853A (en) * | 2014-07-04 | 2014-10-22 | 南京航空航天大学 | Stratified positive material of lithium ion battery and preparation method of material |
| CN104937746A (en) * | 2012-12-14 | 2015-09-23 | 塔拉尼斯公司 | Method for producing a coating material for coating electrode carriers and coating material in granule form |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101384881B1 (en) * | 2010-11-02 | 2014-04-15 | 한국전자통신연구원 | Lithium rechargeable battery |
-
2016
- 2016-07-20 CN CN201610572497.3A patent/CN106058192B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102498594A (en) * | 2009-07-25 | 2012-06-13 | 赢创德固赛有限公司 | Coating method for producing electrodes for electrical energy stores |
| CN102569780A (en) * | 2012-02-28 | 2012-07-11 | 南京航空航天大学 | Method for preparing lithium ion battery cathode material with layered structure |
| CN104937746A (en) * | 2012-12-14 | 2015-09-23 | 塔拉尼斯公司 | Method for producing a coating material for coating electrode carriers and coating material in granule form |
| CN104112853A (en) * | 2014-07-04 | 2014-10-22 | 南京航空航天大学 | Stratified positive material of lithium ion battery and preparation method of material |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106058192A (en) | 2016-10-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106058192B (en) | A kind of coating modification layered cathode material of lithium ion battery and preparation method thereof | |
| US20140315081A1 (en) | Composite electrode material for lithium ion battery and preparation method thereof | |
| CN111435761B (en) | All-solid-state lithium ion battery and hot-pressing preparation method of multilayer electrolyte membrane thereof | |
| KR101650569B1 (en) | Lithium transition metal cathode active material, preparation method thereof, and lithium secondary battery comprising the same | |
| CN113451580B (en) | Interfacial layer and lithium ion battery comprising same | |
| WO2013121624A1 (en) | Negative electrode for lithium secondary battery and method for manufacturing same | |
| JP2007042601A (en) | Carbon electrode, production method therefor and nonaqueous electrolyte secondary battery | |
| KR20020011108A (en) | Carbon substrate, anode for lithium ion rechargeable battery and lithium ion rechargeable battery | |
| JP7413482B2 (en) | Manufacturing method for lithium ion battery negative electrode material | |
| CN112331830A (en) | Preparation method of graphene-coated nickel-cobalt-manganese ternary positive electrode material | |
| Parikh et al. | Operando analysis of gas evolution in TiNb2O7 (TNO)-based anodes for advanced high-energy lithium-ion batteries under fast charging | |
| CN110911741B (en) | Carbon oxide sphere doped solid polymer electrolyte membrane and preparation method and application thereof | |
| CN110534816B (en) | Fibrous flexible rechargeable zinc-manganese battery based on multi-valence manganese oxide | |
| CN113299982A (en) | In-situ polymerization electrolyte, method for preparing in-situ all-solid-state battery by adopting same and in-situ all-solid-state battery | |
| KR101490294B1 (en) | Positive electrode active material and method of manufacturing the same, and electrochemical device having the positive electrode | |
| CN111017903A (en) | High-performance carbon anode PAN hard carbon material and preparation method thereof | |
| CN114512708A (en) | Preparation method and application of lithium ion composite solid electrolyte | |
| CN108269992A (en) | A kind of composite anode material of high-capacity lithium ion battery and preparation method thereof | |
| CN111900458A (en) | Composite solid electrolyte and preparation method thereof | |
| KR102676486B1 (en) | Anode active material composition, method for preparing the same, and rechargeable lithium battery comprising the same | |
| JP2007018794A (en) | Carbon material electrode, its manufacturing method and nonaqueous electrolyte secondary battery | |
| CN110931759B (en) | Al (aluminum)2O3Coated Co-W double-doped LiNiO2Lithium ion battery anode material and preparation method thereof | |
| KR101888230B1 (en) | Silicon-based anode active material and its fabrication method | |
| JP6613952B2 (en) | Positive electrode active material, and positive electrode and lithium ion secondary battery using the same | |
| CN114220975A (en) | Lithium-rich manganese-based positive pole piece and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |