CN109148852A - A kind of preparation method and its material of the graphite cathode material improving covering property - Google Patents
A kind of preparation method and its material of the graphite cathode material improving covering property Download PDFInfo
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- CN109148852A CN109148852A CN201810939164.9A CN201810939164A CN109148852A CN 109148852 A CN109148852 A CN 109148852A CN 201810939164 A CN201810939164 A CN 201810939164A CN 109148852 A CN109148852 A CN 109148852A
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- petroleum coke
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 49
- 239000010439 graphite Substances 0.000 title claims abstract description 49
- 239000010406 cathode material Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000000463 material Substances 0.000 title description 20
- 239000002006 petroleum coke Substances 0.000 claims abstract description 57
- 239000002245 particle Substances 0.000 claims abstract description 50
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 33
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 33
- 235000021355 Stearic acid Nutrition 0.000 claims abstract description 25
- 238000005087 graphitization Methods 0.000 claims abstract description 25
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims abstract description 25
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000008117 stearic acid Substances 0.000 claims abstract description 25
- 230000004048 modification Effects 0.000 claims abstract description 19
- 238000012986 modification Methods 0.000 claims abstract description 19
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 18
- 239000011248 coating agent Substances 0.000 claims abstract description 18
- 238000000576 coating method Methods 0.000 claims abstract description 18
- 238000005253 cladding Methods 0.000 claims abstract description 16
- 239000011246 composite particle Substances 0.000 claims abstract description 14
- 230000000802 nitrating effect Effects 0.000 claims abstract description 11
- 238000001816 cooling Methods 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 16
- 230000008569 process Effects 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 8
- 230000003197 catalytic effect Effects 0.000 claims description 7
- 230000032050 esterification Effects 0.000 claims description 7
- 238000005886 esterification reaction Methods 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 7
- 238000007493 shaping process Methods 0.000 claims description 7
- 238000003801 milling Methods 0.000 claims description 6
- 230000008859 change Effects 0.000 claims description 3
- 239000003208 petroleum Substances 0.000 claims description 2
- 235000019422 polyvinyl alcohol Nutrition 0.000 claims 4
- DCXXMTOCNZCJGO-UHFFFAOYSA-N tristearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(OC(=O)CCCCCCCCCCCCCCCCC)COC(=O)CCCCCCCCCCCCCCCCC DCXXMTOCNZCJGO-UHFFFAOYSA-N 0.000 claims 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims 1
- 229910052738 indium Inorganic materials 0.000 claims 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims 1
- 239000003607 modifier Substances 0.000 claims 1
- 229910052760 oxygen Inorganic materials 0.000 claims 1
- 239000001301 oxygen Substances 0.000 claims 1
- 229910003437 indium oxide Inorganic materials 0.000 abstract description 10
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 abstract description 10
- 230000000694 effects Effects 0.000 abstract description 5
- 238000004939 coking Methods 0.000 abstract description 4
- 230000007547 defect Effects 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 description 15
- 229910052744 lithium Inorganic materials 0.000 description 7
- 239000011295 pitch Substances 0.000 description 7
- 230000006872 improvement Effects 0.000 description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 235000021050 feed intake Nutrition 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 239000000571 coke Substances 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 239000007770 graphite material Substances 0.000 description 3
- 239000011339 hard pitch Substances 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 239000011331 needle coke Substances 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000004087 circulation Effects 0.000 description 2
- 239000007773 negative electrode material Substances 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 238000005899 aromatization reaction Methods 0.000 description 1
- 150000001722 carbon compounds Chemical class 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000010410 dusting Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000009628 steelmaking Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000011366 tin-based material Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
-
- 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
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
-
- 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
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Composite Materials (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses a kind of preparation methods of graphite cathode material for improving covering property, the following steps are included: petroleum coke particles and coating modification agent are mixed, it heats and cladding is carried out to petroleum coke particles and form composite particles, it is cooling, the graphite cathode material for improving covering property can be obtained in graphitization, and wherein coating modification agent is distributed by following parts by weight group: 55-60 parts of pitch, polyvinyl alcohol 20-25 parts stearic acid modified, 5-8 parts of nanometer nitrating indium oxide.Compared with prior art, the present invention carries out coating modification to petroleum coke using pitch, stearic acid modified polyvinyl alcohol, nanometer nitrating indium oxide, reduce the surface tension, softness number and coking value of pitch, also function to the effect of the glutinous plasticising of drop, realize effective coating modification to petroleum coke particles, the defects of reducing the gully of graphite surface, pit after graphitization, improve the graphitization activity and first charge-discharge efficiency and its cyclical stability of graphite.
Description
Technical field
The present invention relates to lithium cell cathode material technical field more particularly to a kind of graphite cathode materials for improving covering property
The preparation method and its material of material.
Background technique
Currently, main lithium ion battery negative material have it is following several: graphitized carbon material, nitride, silica-base material,
Tin-based material, novel alloy, and the negative electrode of lithium ion battery of large-scale commercial only has two major classes, be exactly graphite carbon material and
Lithium titanate (LTO) material.Graphite material good conductivity, crystallinity is higher, has good layer structure, is suitble to the insertion-of lithium
Deintercalation, specific discharge capacity is up to 300mAh/g or more, and for efficiency for charge-discharge 90% or more, irreversible capacity is lower than 50mAh/g.?
Eye future, the development priority of negative electrode material by towards height ratio capacity, high charge-discharge efficiencies, high circulation performance and lower cost side
To development.But since graphite layers are away from small (d002≤0.34nm), cause in charge and discharge process, graphite layers away from change,
It easily causes graphite linings to peel off, dusting, it also occur that lithium ion and organic solvent decompose, and then influences the cycle performance of battery；It is high
Warm pitch is widely used to the modified cladding of graphite cathode due to its excellent performance, but its rheological property is poor, and suitable is low
Viscosity section is relatively narrow；Modified coated graphite carbonaceous aggregate falls off, and excessive oxidation consumption, graphitization activity is low, and degree of graphitization is small,
This brings very big problem to practical application.
In view of this, it is necessory to develop, a kind of rheological characteristic is good and covering property is good, charge/discharge capacity is big, de- lithium specific capacity
The preparation method and its material of the graphite cathode material of improvement covering property high, degree of graphitization is high, cycle life is good.
Summary of the invention
It is an object of the present invention to be directed to the prior art above-mentioned deficiency, provide a kind of rheological characteristic is good and covering property is good,
The graphite cathode material for the improvement covering property that charge/discharge capacity is big, de- lithium specific capacity is high, degree of graphitization is high, cycle life is good
Preparation method and its material.
The technical scheme adopted by the invention to achieve the purpose is as follows:
A kind of preparation method for the graphite cathode material improving covering property, comprising the following steps: by petroleum coke particles and cladding
Modifying agent is mixed, and heats and carries out cladding to petroleum coke particles and forms composite particles, and cooling, improvement can be obtained in graphitization
The graphite cathode material of covering property.
Further, the coating modification agent is distributed by following parts by weight group: 55-60 parts of pitch, stearic acid change
Property 20-25 parts of polyvinyl alcohol, 5-8 parts of nanometer nitrating indium oxide.
Further, the stearic acid modified polyvinyl alcohol by stearic acid and polyvinyl alcohol through catalytic esterification and
, the average molecular weight 16000-18000 of polyvinyl alcohol.
Further, the coating modification agent dosage is the 8-18% of petroleum coke particles total weight.
Further, the petroleum coke particles are using petroleum coke as raw material, and by just breaking, mechanical mill is milled and shaping obtains
The petroleum coke particles of the particle size range 16-19um arrived.
Further, the cladding process includes adjusting speed of agitator 10-100Hz, heating and temperature programming in furnace, journey
Sequence heating was room temperature to 200 DEG C of controls at 0.5-10 hours, and 200 DEG C to 400 DEG C controls were controlled 1-10 hours, 00 DEG C to 600 DEG C
System was at 1-10 hours, and 600 DEG C of thermostatic controls were at 1-10 hours.
Further, described to be cooled to naturally cool to room temperature；Graphite turns to 2000-3000 DEG C of graphitization temperature, when
Between be 8-18 hours.
A kind of stone for the improvement covering property that the preparation method of the graphite cathode material above-mentioned improving covering property is prepared
Black negative electrode material.
Petroleum coke is the decompression residuum of petroleum, through coking plant, cracks coking at 500~550 DEG C and the black that generates
Solid coke, appearance are black or dimmed honeycomb structure, and how oval coke button inner air vent is, and interpenetrates, one
As think that it is the needle containing small graphite crystallization in amorphous carbon body or a kind of macromolecule carbon compound of height aromatisation
Shape or the charcoal body object of granular texture.It is burnt and 3 kinds of needle coke that sponge coke, honeycomb can be divided into.Needle coke: have apparent needle-shaped
Structure and fiber pattern, densification is as fibrous, also known as high-quality coke, high power and ultrahigh power graphite electricity in main function steel-making
Pole, needle coke are mainly that the residual oil high with arene content, non-hydrocarbon impurities content is less is made.Preferred domestic low cost in the present invention
Petroleum coke such as Behavior of High-sulfur Petroleum Coke etc..
Hard pitch (pitch), ring and ball softening point are 95~120 DEG C；In addition, being required according to user, coke-oven plant can be given birth to
Production softening point is 120~250 DEG C of ultrahigh-temperature pitches.It is preferably 250 DEG C of hard pitches of softening point in the present invention.
Compared with prior art, the invention has the benefit that the graphite cathode provided by the invention for improving covering property
The preparation method and its material of material coat petroleum coke using pitch, stearic acid modified polyvinyl alcohol, nanometer nitrating indium oxide
It is modified, the surface tension, softness number and coking value of hard pitch are reduced by stearic acid modified polyvinyl alcohol, and it is glutinous to also function to drop
The effect of plasticising effectively improves the rheological property of hard pitch.Nanometer nitrating indium oxide and stearic acid modified polyvinyl alcohol
Petroleum coke particles are incorporated into pitch and are effectively coated, and are reduced the keys such as C-O, the C=O on graphite material surface, are reduced
After graphitization the defects of the gully of graphite surface, pit, the pattern and uniformity of graphite after cladding are improved, graphite is improved
Graphitization activity, improves the first charge-discharge efficiency and its cyclical stability of graphite cathode material, recharge/discharge cycles
Can also prevent afterwards active material removing and disengaging and inhibit battery capacity or output power conservation rate reduction, for the first time
Discharge capacity is up to 284 or so mAh/g, and reversible capacity is 580mAh/g or so after 100 circulations, and capacity retention ratio is 80% left
The right side takes off lithium specific capacity up to 345.2mAh/g or so, has obtained that rheological characteristic is good and covering property is good, charge/discharge capacity is big, takes off lithium
The graphite cathode material for the improvement covering property that specific capacity is high, degree of graphitization is high, cycle life is good.
Above-mentioned is the general introduction of inventive technique scheme, and below in conjunction with specific embodiment, the present invention will be further described.
Specific embodiment:
In order to which the purpose of the present invention and technical solution and advantage is more clearly understood, make with reference to embodiments specifically
It is bright.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, it is not intended to limit the present invention.
Embodiment 1: the preparation method of the graphite cathode material provided in this embodiment for improving covering property, comprising the following steps:
Petroleum coke particles and coating modification agent are mixed, heats and cladding is carried out to petroleum coke particles and form composite particles, it is cooling,
The graphite cathode material for improving covering property can be obtained in graphitization.Specifically, comprising:
(1) the coating modification agent that petroleum coke particles and weight percent are petroleum coke particles 8% is thrown to reaction kettle, is thrown
It requires to feed intake while stirring when material, obtains mixture, wherein petroleum coke particles are using petroleum coke as raw material, by just broken, mechanical
The petroleum coke particles for the particle size range 16-19um that mill milling and shaping obtain, the parts by weight and group of coating modification agent are divided into drip
Green 550 parts, 25 5 parts of part, nanometer nitrating indium oxide of stearic acid modified polyvinyl alcohol, stearic acid modified polyvinyl alcohol by stearic acid with
Polyvinyl alcohol is obtained through catalytic esterification, the average molecular weight 16000-18000 of polyvinyl alcohol；
(2) adjust speed of agitator 10Hz, heating and temperature programming in furnace, to mixture carry out temperature programming be room temperature extremely
200 DEG C of controls were at 0.5 hour, and 200 DEG C to 400 DEG C controls were at 10 hours, and 00 DEG C to 600 DEG C control was at 1 hour, 600 DEG C of constant temperature
Control was at 10 hours, and in temperature-rise period, the processes such as the softening of mixture experience, melting are realized in conjunction with whipping process to petroleum coke
The cladding of particle, while petroleum coke particles are mutually bonded, and form secondary composite particles；
(3) secondary composite particles are carried out being cooled to room temperature, carries out graphitization processing later, graphite turns to graphitization temperature
2000 DEG C, the time is 18 hours.
The present embodiment also provides the graphite cathode material for the improvement covering property that the above method is prepared.
Embodiment 2: the preparation method and its material of the graphite cathode material provided in this embodiment for improving covering property, including with
Lower step: (1) coating modification agent that petroleum coke particles and weight percent be petroleum coke particles 10% is thrown to reaction kettle, is thrown
It requires to feed intake while stirring when material, obtains mixture, wherein petroleum coke particles are using petroleum coke as raw material, by just broken, mechanical
The petroleum coke particles for the particle size range 16-19um that mill milling and shaping obtain, the parts by weight and group of coating modification agent are divided into drip
Green 60 parts, 20 8 parts of part, nanometer nitrating indium oxide of stearic acid modified polyvinyl alcohol, stearic acid modified polyvinyl alcohol by stearic acid with
Polyvinyl alcohol is obtained through catalytic esterification, the average molecular weight 16000-18000 of polyvinyl alcohol；
(2) adjust speed of agitator 100Hz, heating and temperature programming in furnace, to mixture carry out temperature programming be room temperature extremely
200 DEG C of controls were at 10 hours, and 200 DEG C to 400 DEG C controls were at 1 hour, and 00 DEG C to 600 DEG C control was at 10 hours, 600 DEG C of constant temperature controls
System was at 1 hour, and in temperature-rise period, the processes such as the softening of mixture experience, melting are realized in conjunction with whipping process to petroleum coke
The cladding of grain, while petroleum coke particles are mutually bonded, and form secondary composite particles；
(3) secondary composite particles are carried out being cooled to room temperature, carries out graphitization processing later, graphite turns to graphitization temperature
2500 DEG C, the time is 18 hours.
Embodiment 3: the preparation method and its material of the graphite cathode material provided in this embodiment for improving covering property, including with
Lower step: (1) coating modification agent that petroleum coke particles and weight percent be petroleum coke particles 18% is thrown to reaction kettle, is thrown
It requires to feed intake while stirring when material, obtains mixture, wherein petroleum coke particles are using petroleum coke as raw material, by just broken, mechanical
The petroleum coke particles for the particle size range 16-19um that mill milling and shaping obtain, the parts by weight and group of coating modification agent are divided into drip
Green 58 parts, 22 6 parts of part, nanometer nitrating indium oxide of stearic acid modified polyvinyl alcohol, stearic acid modified polyvinyl alcohol by stearic acid with
Polyvinyl alcohol is obtained through catalytic esterification, the average molecular weight 16000-18000 of polyvinyl alcohol；
(2) adjust speed of agitator 60Hz, heating and temperature programming in furnace, to mixture carry out temperature programming be room temperature extremely
200 DEG C of controls were at 5 hours, and 200 DEG C to 400 DEG C controls were at 6 hours, and 00 DEG C to 600 DEG C control was at 5 hours, 600 DEG C of thermostatic controls
At 3 hours, in temperature-rise period, the processes such as the softening of mixture experience, melting were realized in conjunction with whipping process to petroleum coke particles
Cladding, while petroleum coke particles are mutually bonded, and form secondary composite particles；
(3) secondary composite particles are carried out being cooled to room temperature, carries out graphitization processing later, graphite turns to graphitization temperature
3000 DEG C, the time is 8 hours.
Embodiment 4: the preparation method and its material of the graphite cathode material provided in this embodiment for improving covering property, including with
Lower step: (1) coating modification agent that petroleum coke particles and weight percent be petroleum coke particles 13% is thrown to reaction kettle, is thrown
It requires to feed intake while stirring when material, obtains mixture, wherein petroleum coke particles are using petroleum coke as raw material, by just broken, mechanical
The petroleum coke particles for the particle size range 16-19um that mill milling and shaping obtain, the parts by weight and group of coating modification agent are divided into drip
Green 58 parts, 23 5 parts of part, nanometer nitrating indium oxide of stearic acid modified polyvinyl alcohol, stearic acid modified polyvinyl alcohol by stearic acid with
Polyvinyl alcohol is obtained through catalytic esterification, the average molecular weight 16000-18000 of polyvinyl alcohol；
(2) adjust speed of agitator 80Hz, heating and temperature programming in furnace, to mixture carry out temperature programming be room temperature extremely
200 DEG C of controls were at 3 hours, and 200 DEG C to 400 DEG C controls were at 8 hours, and 00 DEG C to 600 DEG C control was at 2 hours, 600 DEG C of thermostatic controls
At 7 hours, in temperature-rise period, the processes such as the softening of mixture experience, melting were realized in conjunction with whipping process to petroleum coke particles
Cladding, while petroleum coke particles are mutually bonded, and form secondary composite particles；
(3) secondary composite particles are carried out being cooled to room temperature, carries out graphitization processing later, graphite turns to graphitization temperature
2600 DEG C, the time is 14 hours.
Embodiment 5: the preparation method and its material of the graphite cathode material provided in this embodiment for improving covering property, including with
Lower step: (1) coating modification agent that petroleum coke particles and weight percent be petroleum coke particles 10% is thrown to reaction kettle, is thrown
It requires to feed intake while stirring when material, obtains mixture, wherein petroleum coke particles are using petroleum coke as raw material, by just broken, mechanical
The petroleum coke particles for the particle size range 16-19um that mill milling and shaping obtain, the parts by weight and group of coating modification agent are divided into drip
Green 55 parts, 21 7 parts of part, nanometer nitrating indium oxide of stearic acid modified polyvinyl alcohol, stearic acid modified polyvinyl alcohol by stearic acid with
Polyvinyl alcohol is obtained through catalytic esterification, the average molecular weight 16000-18000 of polyvinyl alcohol；
(2) adjust speed of agitator 35Hz, heating and temperature programming in furnace, to mixture carry out temperature programming be room temperature extremely
200 DEG C of controls were at 10 hours, and 200 DEG C to 400 DEG C controls were at 3 hours, and 00 DEG C to 600 DEG C control was at 6 hours, 600 DEG C of constant temperature controls
System was at 5 hours, and in temperature-rise period, the processes such as the softening of mixture experience, melting are realized in conjunction with whipping process to petroleum coke
The cladding of grain, while petroleum coke particles are mutually bonded, and form secondary composite particles；
(3) secondary composite particles are carried out being cooled to room temperature, carries out graphitization processing later, graphite turns to graphitization temperature
3000 DEG C, the time is 11 hours.
According to the disclosure and teachings of the above specification, those skilled in the art in the invention can also be to above-mentioned embodiment party
Formula is changed and is modified.Therefore, the invention is not limited to the specific embodiments disclosed and described above, to of the invention
Some modifications and changes should also be as falling into the scope of the claims of the present invention.In addition, although being used in this specification
Some specific terms, these terms are merely for convenience of description, does not limit the present invention in any way.
Claims (8)
1. a kind of preparation method for the graphite cathode material for improving covering property, which comprises the following steps: by petroleum coke
Grain is mixed with coating modification agent, heats and carries out cladding to petroleum coke particles and forms composite particles, cooling, graphitization
Obtain improving the graphite cathode material of covering property.
2. improving the preparation method of the graphite cathode material of covering property as described in claim 1, which is characterized in that the cladding
Modifying agent is distributed by following parts by weight group: 55-60 parts of pitch, polyvinyl alcohol 20-25 parts stearic acid modified, nanometer nitrating oxygen
Change indium 5-8 parts.
3. improving the preparation method of the graphite cathode material of covering property as claimed in claim 2, which is characterized in that the tristearin
Sour modified polyvinylalcohol is obtained by stearic acid and polyvinyl alcohol through catalytic esterification, the average molecular weight 16000- of polyvinyl alcohol
18000。
4. improving the preparation method of the graphite cathode material of covering property as described in claim 1, which is characterized in that the cladding
Amount of modifier is the 8-18% of petroleum coke particles total weight.
5. improving the preparation method of the graphite cathode material of covering property as described in claim 1, which is characterized in that the petroleum
Burnt particle is using petroleum coke as raw material, by the petroleum coke for the particle size range 16-19um that just broken, mechanical mill milling and shaping obtain
Particle.
6. improving the preparation method of the graphite cathode material of covering property as described in claim 1, which is characterized in that the cladding
Process includes adjusting speed of agitator 10-100Hz, heating and temperature programming in furnace, and temperature programming is that room temperature to 200 DEG C of controls exist
0.5-10 hours, at 1-10 hour, 00 DEG C to 600 DEG C controlled 600 DEG C of thermostatic controls at 1-10 hours for 200 DEG C to 400 DEG C controls
At 1-10 hours.
7. improving the preparation method of the graphite cathode material of covering property as described in claim 1, which is characterized in that the cooling
To naturally cool to room temperature；Graphite turns to 2000-3000 DEG C of graphitization temperature, and the time is 8-18 hours.
8. what a kind of preparation method of the graphite cathode material as claimed in claim 1 for improving covering property was prepared changes
The graphite cathode material of kind covering property.
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| CN112750988A (en) * | 2019-10-29 | 2021-05-04 | 宝武炭材料科技有限公司 | Liquid-coated oil composition and preparation method and application thereof |
| CN113372137A (en) * | 2020-06-11 | 2021-09-10 | 吉林炭素有限公司 | Graphite electrode green body brushing slurry coating formula |
| CN114597533A (en) * | 2022-03-24 | 2022-06-07 | 广东凯金新能源科技股份有限公司 | Method for recycling negative electrode graphite of lithium ion battery |
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