CN110429275A - The preparation method and carbon coating tertiary cathode material of carbon coating tertiary cathode material - Google Patents
The preparation method and carbon coating tertiary cathode material of carbon coating tertiary cathode material Download PDFInfo
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- CN110429275A CN110429275A CN201910794347.0A CN201910794347A CN110429275A CN 110429275 A CN110429275 A CN 110429275A CN 201910794347 A CN201910794347 A CN 201910794347A CN 110429275 A CN110429275 A CN 110429275A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 100
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 100
- 239000010406 cathode material Substances 0.000 title claims abstract description 94
- 238000000576 coating method Methods 0.000 title claims abstract description 64
- 239000011248 coating agent Substances 0.000 title claims abstract description 63
- 238000002360 preparation method Methods 0.000 title claims abstract description 42
- 239000000463 material Substances 0.000 claims abstract description 24
- 239000003960 organic solvent Substances 0.000 claims abstract description 24
- 150000001875 compounds Chemical class 0.000 claims abstract description 21
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 18
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 18
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 12
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 12
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 8
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- 235000006408 oxalic acid Nutrition 0.000 claims description 6
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 3
- 229910013421 LiNixCoyMn1-x-yO2 Inorganic materials 0.000 claims description 3
- 229910013427 LiNixCoyMn1−x−yO2 Inorganic materials 0.000 claims description 3
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 3
- 239000001630 malic acid Substances 0.000 claims description 3
- 235000011090 malic acid Nutrition 0.000 claims description 3
- 238000005516 engineering process Methods 0.000 abstract description 4
- 239000002131 composite material Substances 0.000 description 16
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 10
- 239000007789 gas Substances 0.000 description 10
- 238000000034 method Methods 0.000 description 10
- 229910001228 Li[Ni1/3Co1/3Mn1/3]O2 (NCM 111) Inorganic materials 0.000 description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 5
- 229910052786 argon Inorganic materials 0.000 description 5
- 229910052744 lithium Inorganic materials 0.000 description 5
- 229910052573 porcelain Inorganic materials 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 230000001681 protective effect Effects 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000010792 warming Methods 0.000 description 4
- 239000002023 wood Substances 0.000 description 4
- 238000001514 detection method Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 229910032387 LiCoO2 Inorganic materials 0.000 description 1
- 229910052493 LiFePO4 Inorganic materials 0.000 description 1
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 description 1
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 235000008429 bread Nutrition 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- -1 manganese class compound Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 238000011895 specific detection Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 230000000007 visual effect Effects 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
- H01M10/04—Construction or manufacture in general
- H01M10/0422—Cells or battery with cylindrical casing
- H01M10/0427—Button cells
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
-
- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The present invention relates to battery technology fields, preparation method and carbon coating tertiary cathode material in particular to carbon coating tertiary cathode material；The preparation method of the carbon coating tertiary cathode material includes the tertiary cathode material that will be dried, organic carbon source and organic solvent compound, is placed under the conditions of temperature is 240-350 DEG C and is heat-treated.The preparation method of carbon coating tertiary cathode material provided by the invention is not easy that ternary material is made to generate miscellaneous phase, and carbon coating tertiary cathode material obtained has good cycle performance and high rate performance.
Description
Technical field
The present invention relates to battery technology fields, in particular to the preparation method and carbon of carbon coating tertiary cathode material
Coat tertiary cathode material.
Background technique
Lithium ion battery is answered the advantages that long circulating performance and environment friendly and widely because of its high-energy density
With.The positive electrode for being presently available for lithium ion battery has: LiCoO2, nickel cobalt binary, nickel cobalt manganese, manganese class compound, LiFePO4
Deng.As lithium battery is using more and more extensive, the ternary NCM material with high-energy density enters the visual field of people.
The method for the preparation ternary NCM that the relevant technologies provide exist be easy to make ternary material generation miscellaneous phase the problems such as.
Summary of the invention
The purpose of the present invention is to provide the preparation method of carbon coating tertiary cathode material and carbon coating tertiary cathode material,
This method is not easy that ternary material is made to generate miscellaneous phase.
The present invention is implemented as follows:
In a first aspect, the embodiment of the present invention provides a kind of preparation method of carbon coating tertiary cathode material, comprising: will dry
Tertiary cathode material, organic carbon source and organic solvent compound, be placed in temperature be 240-350 DEG C under the conditions of be heat-treated.
In alternative embodiments, the heating rate of heat treatment is 1 DEG C/min-5 DEG C/min.
In alternative embodiments, the preparation of dry tertiary cathode material, organic carbon source and organic solvent compound
Method includes: that tertiary cathode material and organic carbon source are dissolved in organic solvent, then is dried.
In alternative embodiments, dry temperature is 150-200 DEG C.
In alternative embodiments, tertiary cathode material LiNixCoyMn1-x-yO2；Wherein, 0 < x < 1,0 < y < 1, and x+
y<1。
In alternative embodiments, organic carbon source includes at least one in oxalic acid, malonic acid, malic acid and citric acid
Kind.
In alternative embodiments, organic solvent includes at least one of benzene, toluene and dimethylbenzene.
In alternative embodiments, the quality of tertiary cathode material is 0.02 times to 50 times of the quality of organic carbon source.
In alternative embodiments, the time of heat treatment is 2-8h.
Second aspect, the embodiment of the present invention provide a kind of carbon coating tertiary cathode material, are appointed by aforementioned embodiments
The preparation method preparation of one carbon coating tertiary cathode material.
The beneficial effect of the preparation method of carbon coating tertiary cathode material of the invention includes: provided in an embodiment of the present invention
The preparation method of tertiary cathode material in the dry tertiary cathode material of heat treatment, organic carbon source and organic solvent compound,
Temperature is relatively low, can reduce the problem of tertiary cathode material redox occurs and generates miscellaneous phase.
The beneficial effect of carbon coating tertiary cathode material of the invention includes: that the carbon coating ternary material is by above-mentioned system
Preparation Method preparation, the miscellaneous phase of the carbon coating positive electrode is few.
Detailed description of the invention
In order to illustrate the technical solution of the embodiments of the present invention more clearly, below will be to needed in the embodiment attached
Figure is briefly described, it should be understood that the following drawings illustrates only certain embodiments of the present invention, therefore is not construed as pair
The restriction of range for those of ordinary skill in the art without creative efforts, can also be according to this
A little attached drawings obtain other relevant attached drawings.
Fig. 1 is the XRD diagram of the tertiary cathode material and the carbon coating tertiary cathode material prepared in embodiment 1；
Fig. 2 is the charging and discharging curve of the carbon coating tertiary cathode material for preparing under 200mA/g current density in embodiment 1
Figure；
Fig. 3 is the curve graph of the carbon coating tertiary cathode material for preparing under different multiplying in embodiment 1；
Fig. 4 is the cyclic curve of the carbon coating tertiary cathode material for preparing under 200mA/g current density in embodiment 1
Figure.
Specific embodiment
It in order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below will be in the embodiment of the present invention
Technical solution be clearly and completely described.The person that is not specified actual conditions in embodiment, according to normal conditions or manufacturer builds
The condition of view carries out.Agents useful for same or instrument, which are not specified, generates manufacturer person, is the conventional production that can be obtained by commercially available purchase
Product.
The preparation method and carbon coating tertiary cathode material of carbon coating tertiary cathode material of the invention are made into one below
The detailed description of step.
The preparation method of carbon coating tertiary cathode material of the invention includes: by dry tertiary cathode material, organic carbon
Source and organic solvent compound are placed under the conditions of temperature is 240-350 DEG C and are heat-treated.
The present invention exists the temperature control for being heat-treated dry tertiary cathode material, organic carbon source and organic solvent compound
350 DEG C and hereinafter, can reduce tertiary cathode material occur redox, reduce the generation of miscellaneous phase, can ensure that carbon packet obtained
Coated positive pole material has stable, uniform carbon coating structure, to improve the cycle performance and high rate performance of tertiary cathode material.
Further, the heating rate that the present invention is heat-treated is 1 DEG C/min-5 DEG C/min, under lesser heating rate,
Guarantee the compactness and stability of carbon coating structure, to improve the cycle performance and high rate performance of ternary upgrading material.
Still further, the time that the present invention is heat-treated can be 2-8h；The energy under heat treatment time provided by the invention
Enough tertiary cathode materials that further reduces are oxidized reduction, reduce the generation of miscellaneous phase, have carbon coating knot with further improve
The cycle performance and high rate performance of the tertiary cathode material of structure.
Heat treatment in the present invention can place dry tertiary cathode material, organic carbon source and organic solvent compound
In porcelain boat, it is heat-treated in tube furnace；It further, can be using protection gas when being heat-treated in tube furnace
Body is protected, such as: nitrogen or argon gas.
The preparation method of the tertiary cathode material of drying in the present invention, organic carbon source and organic solvent compound includes:
Tertiary cathode material and organic carbon source are dissolved in organic solvent, then are dried.
It is possible to further which tertiary cathode material and organic carbon source are successively dissolved into organic solvent, stirring to mud
Shape, re-dry；Tertiary cathode material and organic carbon source are successively dissolved in organic solvent, also can be reduced the oxygen of tertiary cathode material
Change reduction, reduces miscellaneous phase and generate, and subsequent dissolution organic carbon source can be made to form more stable, uniform carbon coating structure, with
Make tertiary cathode material that there is good cycle performance and high rate performance.
The method that the present invention dries tertiary cathode material, organic carbon source and organic solvent compound includes vacuum drying, is done
Dry temperature is 150-200 DEG C；It is dried under drying temperature provided by the invention, tertiary cathode material can be reduced dry
Dry is that redox reaction occurs, to reduce the generation of miscellaneous phase.
Further, the dry time can be greater than 4h, so that compound sufficiently dry, helps to make subsequent heat treatment
It is the carbon coating structure of carbon coating tertiary cathode material is more uniform, stable.
Tertiary cathode material in the present invention is LiNixCoyMn1-x-yO2；Wherein, 0 < x < 1,0 < y < 1, and x+y < 1；It is above-mentioned
Tertiary cathode material for example can be ternary NCM811 or ternary NCM532 etc..
Organic carbon source of the invention includes at least one of oxalic acid, malonic acid, malic acid and citric acid.
Organic solvent of the invention includes at least one of benzene, toluene and dimethylbenzene.
The quality of tertiary cathode material of the invention is 0.02 times to 50 times of the quality of organic carbon source, i.e. tertiary cathode material
The quality of material and the mass ratio of organic carbon source are 1:50-50:1；The dosage of tertiary cathode material and organic carbon source is controlled upper
It states in range, can be very few to avoid tertiary cathode material, readily volatilized problem can also avoid tertiary cathode material from excessively leading
Organic carbon source is caused not coat uniformly, the problem for avoiding cycle performance improvement bad.
With reference to embodiments to the preparation method and carbon coating tertiary cathode of carbon coating tertiary cathode material of the invention
Material is described in further detail.
Embodiment 1
It by 1.5g ternary NCM811 and 1g oxalic acid, is successively dissolved into toluene, stirring is in muddy.
Above-mentioned muddy compound is placed into vacuum oven, 180 DEG C of dry 6h.
The tertiary cathode material, organic carbon source and organic solvent compound that obtain after above-mentioned drying are placed in porcelain boat,
Argon gas is passed through in tube furnace as protective gas, 5 DEG C/min is warming up to 265 DEG C, keeps the temperature 3h, obtains C@NCM811 composite wood
Expect to get carbon coating positive electrode is arrived.
Electrode slice is made in above-mentioned C@NCM811 composite material and button cell test electrical property is made in lithium piece collocation.
Embodiment 2
It by 2g ternary NCM622 and 1.5g oxalic acid, is successively dissolved into toluene, stirring is in muddy.
Above-mentioned muddy compound is placed into vacuum oven, 200 DEG C of dry 5h.
The tertiary cathode material, organic carbon source and organic solvent compound that obtain after above-mentioned drying are placed in porcelain boat,
Argon gas is passed through in tube furnace as protective gas, 2 DEG C/min is warming up to 240 DEG C, keeps the temperature 2.5h, obtains C@NCM622 composite wood
Expect to get carbon coating positive electrode is arrived.
Electrode slice is made in above-mentioned C@NCM622 composite material and button cell test electrical property is made in lithium piece collocation.
Embodiment 3
It by 1.2g ternary NCM523 and 1g malonic acid, is successively dissolved into benzene, stirring is in muddy.
Above-mentioned muddy compound is placed into vacuum oven, 150 DEG C of dry 5.5h.
The tertiary cathode material, organic carbon source and organic solvent compound that obtain after above-mentioned drying are placed in porcelain boat,
Argon gas is passed through in tube furnace as protective gas, 1 DEG C/min is warming up to 280 DEG C, keeps the temperature 8h, obtains C@NCM523 composite wood
Expect to get carbon coating positive electrode is arrived.
Electrode slice is made in above-mentioned C@NCM523 composite material and button cell test electrical property is made in lithium piece collocation.
Embodiment 4
By the mixture of 2.5g ternary NCM111 and 1.6g oxalic acid and citric acid, it is successively dissolved into the mixed of toluene and dimethylbenzene
It closes in being easy, stirring is in muddy.
Above-mentioned muddy compound is placed into vacuum oven, 160 DEG C of dry 5h.
The tertiary cathode material, organic carbon source and organic solvent compound that obtain after above-mentioned drying are placed in porcelain boat,
Argon gas is passed through in tube furnace as protective gas, 4 DEG C/min is warming up to 350 DEG C, keeps the temperature 2h, obtains C@NCM111 composite wood
Expect to get carbon coating positive electrode is arrived.
Electrode slice is made in above-mentioned C@NCM111 composite material and button cell test electrical property is made in lithium piece collocation.
Tertiary cathode material to embodiment 1 and the carbon coating tertiary cathode material prepared carry out X-ray diffraction point
Analysis, obtains the result of Fig. 1；By the result of Fig. 1 it is found that the XRD diagram of two kinds of materials does not have significant difference, main cause is NCM table
It is agraphitic carbon that bread, which covers carbon material, and without apparent characteristic peak, therefore C@NCM composite material only shows the characteristic peak of NCM main material.
The carbon coating ternary material of tertiary cathode material and preparation to embodiment 1 carries out charge and discharge electro-detection, detection knot
Fruit sees Fig. 2；By Fig. 2 result it is found that C@NCM composite material and the charge and discharge platform of NCM tertiary cathode material are essentially identical, but hold
Measure it is lower, the main reason is that the main function of carbon coating in the composite is the structure for stablizing NCM, to the contribution of capacity compared with
It is low, therefore the gram volume of composite material is lower.
The carbon coating ternary material of tertiary cathode material and preparation to embodiment 1 carries out multiplying power detection, obtains Fig. 3's
As a result；By Fig. 3 result it is found that C NCM composite material is lower relative to NCM tertiary cathode material compared with capacity under low range, when
When multiplying power is greater than 2C, the capacity of C@NCM composite material is higher than NCM tertiary cathode material, and carbon coating layer improves NCM tertiary cathode
The high rate performance of material.
The carbon coating ternary material of tertiary cathode material and preparation to embodiment 1 carries out loop test, test result
See Fig. 4；By Fig. 4 result it is found that with cycle-index increase, the capacity of C@NCM composite material is increasingly greater than NCM tertiary cathode
The capacity of material, C@NCM composite material cyclical stability with higher, the main reason is that carbon coating layer prevents NCM ternary
The structure collapses of positive electrode, and then improve its cyclical stability.
The method for holding above-mentioned, of the invention preparation carbon coating ternary material, can be by carbon coating in ternary material, moreover it is possible to subtract
Few miscellaneous phase generates, so that carbon coating ternary material has good high rate performance and cycle performance.
By in embodiment 1-4 tertiary cathode material raw material NCM811, NCM622, NCM523, NCM111 and with implement
Carbon coating tertiary cathode material C@NCM811, C@NCM622, C@NCM523, C@NCM111 is made in preparation method in example 1-4
Forthright again and cyclicity is detected respectively, and specific detection method is similar with the relevant technologies, and details are not described herein；It the results are shown in Table 1.
The multiplying power of the carbon coating tertiary cathode material obtained after the tertiary cathode material raw material of 1 each group embodiment of table and preparation
Property and cyclicity result
By the interpretation of result of table 1 it is found that the carbon coating ternary material of embodiment 1-4 is when multiplying power is greater than 2C, capacity is high
In uncoated tertiary cathode raw material, illustrate that the carbon coating tertiary cathode material of method preparation of the invention has preferable times
It is forthright.
By the interpretation of result of table 1 it is found that increase of the carbon coating ternary material of embodiment 1-4 with cycle-index, capacity
Greater than uncoated tertiary cathode raw material, it is preferable to illustrate that the carbon coating tertiary cathode material of method preparation of the invention has
Cycle performance.
In conclusion the preparation method of tertiary cathode material provided in an embodiment of the present invention is being heat-treated dry ternary just
When pole material, organic carbon source and organic solvent compound, temperature is relatively low, can reduce tertiary cathode material and oxidation occurs also
It is former and the problem of generate miscellaneous phase.
The miscellaneous phase that the carbon coating tertiary cathode material of method preparation of the invention generates is few, have good times it is forthright and follow
Ring performance.
The foregoing is only a preferred embodiment of the present invention, is not intended to restrict the invention, for the skill of this field
For art personnel, the invention may be variously modified and varied.All within the spirits and principles of the present invention, made any to repair
Change, equivalent replacement, improvement etc., should all be included in the protection scope of the present invention.
Claims (10)
1. a kind of preparation method of carbon coating tertiary cathode material characterized by comprising
By dry tertiary cathode material, organic carbon source and organic solvent compound, it is placed in heat under the conditions of temperature is 240-350 DEG C
Processing.
2. the preparation method of carbon coating tertiary cathode material according to claim 1, which is characterized in that the heat treatment
Heating rate is 1 DEG C/min-5 DEG C/min.
3. the preparation method of carbon coating tertiary cathode material according to claim 1, which is characterized in that dry ternary is just
The preparation method of pole material, organic carbon source and organic solvent compound includes: to be dissolved in tertiary cathode material and organic carbon source
In organic solvent, then it is dried.
4. the preparation method of carbon coating tertiary cathode material according to claim 3, which is characterized in that the temperature of the drying
Degree is 150-200 DEG C.
5. the preparation method of carbon coating tertiary cathode material according to claim 1, which is characterized in that the tertiary cathode
Material is LiNixCoyMn1-x-yO2；Wherein, 0 < x < 1,0 < y < 1, and x+y < 1.
6. the preparation method of carbon coating tertiary cathode material according to claim 1, which is characterized in that the organic carbon source
Including at least one of oxalic acid, malonic acid, malic acid and citric acid.
7. the preparation method of carbon coating tertiary cathode material according to claim 1, which is characterized in that the organic solvent
Including at least one of benzene, toluene and dimethylbenzene.
8. the preparation method of carbon coating tertiary cathode material according to claim 1, which is characterized in that the tertiary cathode
The quality of material is 0.02 times to 50 times of the quality of the organic carbon source.
9. the preparation method of carbon coating tertiary cathode material according to claim 1, which is characterized in that the heat treatment
Time is 2-8h.
10. a kind of carbon coating tertiary cathode material, which is characterized in that it is by the described in any item carbon coatings of claim 1-9
The preparation method preparation of tertiary cathode material.
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