CN109346707A - A kind of cathode material of lithium ion battery and preparation method thereof and lithium ion battery - Google Patents
A kind of cathode material of lithium ion battery and preparation method thereof and lithium ion battery Download PDFInfo
- Publication number
- CN109346707A CN109346707A CN201811358809.6A CN201811358809A CN109346707A CN 109346707 A CN109346707 A CN 109346707A CN 201811358809 A CN201811358809 A CN 201811358809A CN 109346707 A CN109346707 A CN 109346707A
- Authority
- CN
- China
- Prior art keywords
- presoma
- ion battery
- lithium ion
- preparation
- micro crystal
- 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.)
- Withdrawn
Links
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
- H01M4/58—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
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
-
- 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
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
-
- 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
- H01M2004/027—Negative 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
Abstract
The present invention relates to field of lithium, discloses a kind of cathode material of lithium ion battery and preparation method thereof and lithium ion battery, method include: to close micro crystal graphite powder and acid-mixed to carry out hot dipping processing, washed after hot dipping processing, obtain presoma a；By presoma a and binder, catalyst and auxiliary agent ball milling mixing, briquetting is carried out, presoma b is obtained；Presoma b is sintered, then high temperature graphitization in protective atmosphere, obtains presoma c；Presoma c is crushed, nodularization, classification, obtains presoma d；By presoma d and carbon source hot mixing, presoma e is obtained；By presoma e under an inert atmosphere high temperature sintering, screening, obtain cathode material of lithium ion battery.Using the microlite ink powder of low-carbon highly acidity, reduce pickling in production process, washing times, using the graphited mode of briquetting is blended, so that micro crystal graphite reconstruction optimizes, the amorphous carbon material of outermost layer cladding improves material coulombic efficiency for the first time.
Description
Technical field
The present invention relates to technical field of lithium batteries more particularly to a kind of cathode material of lithium ion battery and preparation method thereof
And lithium ion battery.
Background technique
Current commercialized lithium ion battery generallys use natural flake graphite or artificial graphite as negative electrode material.But
It is that as negative electrode material, cycle performance is poor for natural flake graphite or artificial graphite.
Natural micro crystal graphite is also known as aphanitic graphite, amorphous graphite or amorphous graphite, by many small graphite in structure
Crystal is constituted, and the higher mineral impurity content of degree of graphitization is high, although being used as lithium ion battery negative material has well
Cycle performance, but the disadvantages that have that coulombic efficiency is low, reversible capacity is low for the first time etc., natural micro crystal graphite is from a wealth of sources, China
Reserves are huge, cheap for opposite mainstream natural flake graphite, if its coulomb for the first time can be improved by processing appropriate
Efficiency and reversible capacity are then expected to be used as to cycle performance and the higher negative electrode of power lithium-ion battery material of production cost requirement
Material.
CN105977489A discloses a kind of lithium ion battery modification of microcrystalline graphite cathode material preparation method, will be natural
Micro crystal graphite is added to agitating ball mill and carries out ball milling, and then filtration drying obtains the graphite composite powder after ball milling, obtained graphite
After powder is mixed with catalyst, pitch, lower heating stirring is vacuumized, graphitization carries out the powdered graphite after cladding at graphitization
Reason, obtains modification of microcrystalline graphite cathode material.But process is tedious, production efficiency is low, while products obtained therefrom performance inconsistency
Larger, the consistency of product is poor, is unfavorable for batch production processing.
Summary of the invention
In view of this, the present invention provides a kind of cathode material of lithium ion battery and preparation method thereof and lithium-ion electrics
Pond, this preparation method is simple, and process is few, and negative electrode material obtained is applied in lithium ion battery, charging capacity and electric discharge
Capacity is larger, and coulombic efficiency is high for the first time, and stability is good.
A kind of preparation method of cathode material of lithium ion battery, method include:
S1. micro crystal graphite powder and acid-mixed are closed and carries out hot dipping processing, washed after hot dipping processing, obtain presoma a；
S2. by the presoma a and binder, catalyst and auxiliary agent ball milling mixing, briquetting is carried out, presoma b is obtained；
S3. the presoma b is sintered, then high temperature graphitization in protective atmosphere, obtains presoma c；
S4. the presoma c is crushed, nodularization, classification, obtains presoma d；
S5. by the presoma d and carbon source hot mixing, presoma e is obtained；
S6. by the presoma e under an inert atmosphere high temperature sintering, screening, obtain cathode material of lithium ion battery.
Preferably, the S2 includes:
Presoma a, binder, catalyst and auxiliary agent are placed according to mass ratio for 50-80:20-30:10-15:5-8
It is 20-30:70-80 by ratio of grinding media to material in ball mill, with pressure is that 10-25MPa carries out briquetting by mixing after ball milling mixing 2-8h,
Obtain presoma b.
Preferably, the bonding agent be one of coal tar pitch, coal tar, phenolic resin, epoxy resin, polyacrylonitrile or
It is a variety of；The catalyst is one of iron chloride, silicon carbide, boron carbide, vanadium oxide or a variety of, and catalyst grain size D50 is 5-
30um。
Preferably, the micro crystal graphite powder is that micro crystal graphite original ore powder chopping fine is ground, and the micro crystal graphite powder is
Low-carbon highly acidity micro crystal graphite powder, the content of graphite of the low-carbon highly acidity micro crystal graphite powder be greater than 90%, it is described micro-
Spar ink raw ore content of graphite is 65-85%.
Preferably, the S1 includes:
It is 5-100um, micro crystal graphite powder of the carbon content greater than 90% and volume ratio hydrofluoric acid: hydrochloric acid=7-9 by D50:
It is mixed in the mix acid liquor of 1-3, wherein mix acid liquor and micro crystal graphite powder liquid consolidate mass ratio as 1.5-5:1, are heated to 45-
75 DEG C, 2.5-3.5h is stirred, filters, much filtrate is washed with water, until washing out liquid PH is greater than 4, much filtrate is filtered, is done
It is dry, obtain presoma a, wherein the fixed carbon content of presoma a is greater than 95%.
Preferably, the S3 includes:
Presoma b is carried out to the low-temperature sintering that temperature is 100-600 DEG C in protective atmosphere, after being sintered 8-11h, will be sintered
Material to carry out temperature be the processing of 2500-3200 DEG C of high temperature graphitization, obtain presoma c；Wherein, the protective atmosphere is nitrogen
Or one of argon gas or a variety of.
Preferably, the S5 includes:
By presoma d and one of pitch, coal tar, phenolic resin, glucose or it is a variety of be in mass ratio 95-85:
5-15 mixes 1.5-2.5h at a temperature of 110-280 DEG C, obtains presoma e.
Preferably, the S6 includes:
By presoma e in one of nitrogen, argon gas and helium or a variety of atmosphere, sintering temperature 750-1300
DEG C, it is sintered 8-30h, material after sintering is sieved, cathode material of lithium ion battery is obtained.
A kind of cathode material of lithium ion battery, the cathode material of lithium ion battery are made by above-mentioned preparation method.
A kind of lithium ion battery, including the negative electrode material as made from any of the above-described preparation method, conductive agent, carboxymethyl cellulose
Plain sodium, butadiene-styrene rubber, water coat the battery pole piece that copper foil is constituted according to mass ratio for 85:5:5:5:100, with opposing metallic lithium electricity
Pond pole piece and electrolyte constitute lithium ion battery.
The present invention provides a kind of cathode material of lithium ion battery and preparation method thereof and lithium ion battery, this method is adopted
With the microlite ink powder of low-carbon highly acidity, pickling, washing times in micro crystal graphite production process are greatly reduced, is effectively controlled
Spent acid, waste liquid output, reduce costs, improve environmental friendliness；It is total using micro crystal graphite, binder, catalyst simultaneously
The graphited mode of briquetting is mixed, so that micro crystal graphite reconstruction optimizes, the product reversible capacity of preparation is greatly promoted, outermost
The amorphous carbon material of layer cladding is also greatly improved material coulombic efficiency for the first time.
Detailed description of the invention
Technical solution in order to illustrate the embodiments of the present invention more clearly, below will be to needed in embodiment description
Attached drawing is briefly described, it should be apparent that, the Characterization result figure that drawings in the following description are some embodiments of the invention,
For those of ordinary skill in the art, without creative efforts, it can also be obtained according to these attached drawings
Other attached drawings.
Fig. 1 is scanning electron microscope to cathode material of lithium ion battery scanning figure；
Fig. 2 is the XRD x ray diffraction map to cathode material of lithium ion battery；
Fig. 3 is battery charging and discharging curve graph.
Specific embodiment
Below in conjunction with the embodiment of the present invention, technical scheme in the embodiment of the invention is clearly and completely described,
Obviously, described embodiments are some of the embodiments of the present invention, instead of all the embodiments.Based on the implementation in the present invention
Example, every other embodiment obtained by those of ordinary skill in the art without making creative efforts belong to
The scope of protection of the invention.
It should be appreciated that ought use in this specification and in the appended claims, term " includes " and "comprising" instruction
Described feature, entirety, step, operation, the presence of element and/or component, but one or more of the other feature, whole is not precluded
Body, step, operation, the presence or addition of element, component and/or its set.
It will be further appreciated that the term "and/or" used in description of the invention and the appended claims is
Refer to any combination and all possible combinations of one or more of associated item listed, and including these combinations.
The preparation method of cathode material of lithium ion battery, comprising:
The raw ore coarse granule for being 65-85% by micro crystal graphite content, is placed in ball mill, 300-500r/min ball milling 5-7h
Afterwards, flotation, drying, magnetic separation are carried out, obtaining D50 is 5-100um, micro crystal graphite powder of the carbon content 90% or more, by crystallite
Graphite composite powder puts into volume ratio hydrofluoric acid: in hydrochloric acid=7-9:1-3 mix acid liquor, 45-75 DEG C heated, stirs 2.5-3.5h,
It filters, much filtrate is washed with water, until washing out liquid PH is greater than 4, much filtrate is filtered, is dried, it is big to obtain fixed carbon content
In 95% presoma a；Presoma a is the micro crystal graphite powder of low-carbon highly acidity, and existing presoma a is generally high neutral carbon
Micro crystal graphite powder, but the micro crystal graphite powder of low-carbon highly acidity is washed into high neutral carbon micro crystal graphite powder and needs to expend greatly
The water and washing lotion of amount can make spent acid, waste liquid output, increase cost, and pollute environment, this method is directly (low by presoma a
The micro crystal graphite of carbon highly acidity) it is utilized；By presoma a, binder, catalyst and auxiliary agent according to mass ratio be 50-80:
20-30:10-15:5-8 is placed in ball mill, wherein bonding agent is coal tar pitch, coal tar, phenolic resin, epoxy resin, poly- third
One of alkene nitrile is a variety of；Catalyst is one of iron chloride, silicon carbide, boron carbide, vanadium oxide or a variety of, catalyst pellets
Degree D50 is 5-30um, and auxiliary agent is generally washing oil, is 20-30:70-80 by ratio of grinding media to material, and revolving speed 150-300r/min, ball milling mixes
After closing 2-8h, mixing is subjected to briquetting with pressure for 10-25MPa, obtains presoma b；By presoma b in nitrogen or argon gas
One or more protective atmospheres, Ventilation Rate 8-11L/min, 2-5 DEG C of heating rate/min, carrying out temperature is 100-600 DEG C
Low-temperature sintering, be sintered 8-11h after, the material of sintering is transferred to graphitizing furnace, is passed through argon gas or nitrogen, Ventilation Rate is
15-25L/min, 7-11 DEG C of heating rate/min, carrying out temperature is the processing of 2500-3200 DEG C of high temperature graphitization, and the processing time is
280-320h, natural cooling cooling, obtains presoma c；Presoma c is crushed, nodularization, classification, being crushed to D50 is 5-
20um, wherein nodularization time 25-35min is classified blower loading frequency 5-8HZ, grade frequency 30-40HZ, obtains presoma d；
A variety of exist in mass ratio by presoma d and one of pitch, coal tar, phenolic resin, glucose or for 95-85:5-15
1.5-2.5h is mixed at a temperature of 110-280 DEG C, obtains presoma e；By presoma e in one of nitrogen, argon gas and helium
Or in a variety of atmosphere, Ventilation Rate 8-12L/min, 4-6 DEG C of heating rate/min, sintering temperature is 750-1300 DEG C, is burnt
8-30h is tied, material after sintering is sieved, cathode material of lithium ion battery is obtained.
Specific embodiment 1
A kind of preparation method of cathode material of lithium ion battery, comprising:
The raw ore coarse granule for being 75% by micro crystal graphite content, is placed in ball mill, after 400r/min ball milling 6h, is floated
Choosing, drying, magnetic separation, obtaining D50 is 5-100um, and carbon content throws micro crystal graphite powder in 90% or more micro crystal graphite powder
Enter volume ratio hydrofluoric acid: in hydrochloric acid=8:2 mix acid liquor, heating 65 DEG C, stir 3h, filter, much filtrate is washed with water, until washing
Liquid PH is greater than 4 out, is filtered, dries to much filtrate, obtains the presoma a that fixed carbon content is greater than 95%；By presoma
A, binder, catalyst and auxiliary agent are that 80:20:10:5 is placed in ball mill according to mass ratio, wherein bonding agent is coal drip
Blueness, catalyst are silicon carbide, and it is 20:80 by ratio of grinding media to material that catalyst grain size D50, which is 5-30um, and auxiliary agent is washing oil, and revolving speed is
After 200r/min, ball milling mixing 3h, mixing is subjected to briquetting with pressure for 15MPa, obtains presoma b；By presoma b in nitrogen
Protective atmosphere, Ventilation Rate 10L/min, 3 DEG C/min of heating rate carry out the low-temperature sintering that temperature is 600 DEG C, are sintered 10h
Afterwards, the material of sintering is transferred to graphitizing furnace, is passed through argon gas, Ventilation Rate 20L/min, 8 DEG C/min of heating rate are carried out
Temperature is 2900 DEG C of high temperature graphitization processing, and the processing time is 300h, and natural cooling cooling obtains presoma c；By presoma c
It is crushed, nodularization, classification, being crushed to D50 is 13um, wherein classification blower loading frequency 6HZ, nodularization time 30min divides
Grade frequency 35HZ, obtains presoma d；With pitch in mass ratio it is that 94:6 mixes 2h at a temperature of 180 DEG C by presoma d, obtains
Presoma e；By presoma e in nitrogen atmosphere, Ventilation Rate 10L/min, 5 DEG C/min of heating rate, sintering temperature is
1200 DEG C, it is sintered 10h, material after sintering is sieved, cathode material of lithium ion battery is obtained.
Specific embodiment 2
A kind of preparation method of cathode material of lithium ion battery, comprising:
The raw ore coarse granule for being 68% by micro crystal graphite content, is placed in ball mill, after 450r/min ball milling 7h, is floated
Choosing, drying, magnetic separation, obtaining D50 is 5-100um, and carbon content throws micro crystal graphite powder in 90% or more micro crystal graphite powder
Enter volume ratio hydrofluoric acid: in hydrochloric acid=8:2 mix acid liquor, heating 65 DEG C, stir 3h, filter, much filtrate is washed with water, until washing
Liquid PH is greater than 4 out, is filtered, dries to much filtrate, obtains the presoma a that fixed carbon content is greater than 95%；By presoma
A, binder, catalyst and auxiliary agent are that 80:30:10:8 is placed in ball mill according to mass ratio, wherein bonding agent is coal drip
Blueness, catalyst are silicon carbide, and it is 30:70 by ratio of grinding media to material that catalyst grain size D50, which is 5-30um, and auxiliary agent is washing oil, and revolving speed is
After 300r/min, ball milling mixing 3h, mixing is subjected to briquetting with pressure for 18MPa, obtains presoma b；By presoma b in nitrogen
Protective atmosphere, Ventilation Rate 10L/min, 3 DEG C/min of heating rate carry out the low-temperature sintering that temperature is 600 DEG C, are sintered 10h
Afterwards, the material of sintering is transferred to graphitizing furnace, is passed through argon gas, Ventilation Rate 20L/min, 8 DEG C/min of heating rate are carried out
Temperature is 2850 DEG C of high temperature graphitization processing, and the processing time is 300h, and natural cooling cooling obtains presoma c；By presoma c
It is crushed, nodularization, classification, being crushed to D50 is 15um, wherein classification blower loading frequency 5HZ, nodularization time 30min divides
Grade frequency 40HZ, obtains presoma d；With pitch in mass ratio it is that 92:8 mixes 2h at a temperature of 200 DEG C by presoma d, obtains
Presoma e；By presoma e in nitrogen atmosphere, Ventilation Rate 10L/min, 5 DEG C/min of heating rate, sintering temperature is
1200 DEG C, it is sintered 10h, material after sintering is sieved, cathode material of lithium ion battery is obtained.
Specific embodiment 3
A kind of preparation method of cathode material of lithium ion battery, comprising:
The raw ore coarse granule for being 65% by micro crystal graphite content, is placed in ball mill, after 300r/min ball milling 7h, is floated
Choosing, drying, magnetic separation, obtaining D50 is 5-100um, and carbon content throws micro crystal graphite powder in 90% or more micro crystal graphite powder
Enter volume ratio hydrofluoric acid: in hydrochloric acid=7:3 mix acid liquor, heating 45 DEG C, stir 3.5h, filter, much filtrate is washed with water, until
It washes out liquid PH and is greater than 4, much filtrate is filtered, is dried, obtain the presoma a that fixed carbon content is greater than 95%；By forerunner
Body a, binder, catalyst and auxiliary agent are that 50:20:10:5 is placed in ball mill according to mass ratio, wherein bonding agent is coal drip
Green and coal tar mixing, catalyst are the mixing of iron chloride and silicon carbide, and catalyst grain size D50 is 5-30um, and auxiliary agent is to wash
Oil is 30:70 by ratio of grinding media to material, after revolving speed 150r/min, ball milling mixing 2h, with pressure is that 10MPa carries out briquetting by mixing, obtains
To presoma b；By presoma b in argon atmosphere, Ventilation Rate 11L/min, 5 DEG C/min of heating rate carry out temperature
The material of sintering is transferred to graphitizing furnace, is passed through nitrogen, Ventilation Rate 25L/ after being sintered 8h for 100 DEG C of low-temperature sintering
Min, 7 DEG C/min of heating rate, carrying out temperature is 2500 DEG C of high temperature graphitization processing, and the processing time is 280h, natural cooling drop
Temperature obtains presoma c；Presoma c is crushed, nodularization, classification, being crushed to D50 is 5um, wherein nodularization time 25min,
It is classified blower loading frequency 8HZ, grade frequency 30HZ, obtains presoma d；Presoma d is mixed with pitch and phenolic resin and is pressed
Mass ratio is that 95:5 mixes 2.5h at a temperature of 280 DEG C, obtains presoma e；By presoma e in argon gas and helium mix atmosphere
In, Ventilation Rate 12L/min, 4 DEG C/min of heating rate, sintering temperature are 750 DEG C, are sintered 30h, carry out to material after sintering
Screening, obtains cathode material of lithium ion battery.
Specific embodiment 4
The raw ore coarse granule for being 85% by micro crystal graphite content, is placed in ball mill, after 500r/min ball milling 5h, is floated
Choosing, drying, magnetic separation, obtaining D50 is 5-100um, and carbon content throws micro crystal graphite powder in 90% or more micro crystal graphite powder
Enter volume ratio hydrofluoric acid: in hydrochloric acid=9:1 mix acid liquor, heating 75 DEG C, stir 2.5h, filter, much filtrate is washed with water, until
It washes out liquid PH and is greater than 4, much filtrate is filtered, is dried, obtain the presoma a that fixed carbon content is greater than 95%；By forerunner
Body a, binder, catalyst and auxiliary agent are that 80:30:15:5 is placed in ball mill according to mass ratio, wherein bonding agent is coal drip
Green, phenolic resin and epoxy resin mixing；Catalyst is the mixing of boron carbide and vanadium oxide, and catalyst grain size D50 is
5-30um, auxiliary agent are washing oil, are 25:75 by ratio of grinding media to material, after revolving speed 220r/min, ball milling mixing 8h, are with pressure by mixing
25MPa carries out briquetting, obtains presoma b；By presoma b in argon atmosphere, Ventilation Rate 8L/min, heating rate
2 DEG C/min, the low-temperature sintering that temperature is 400 DEG C is carried out, after being sintered 11h, the material of sintering is transferred to graphitizing furnace, is passed through argon
Gas, Ventilation Rate 15L/min, 11 DEG C/min of heating rate, carrying out temperature is 3200 DEG C of high temperature graphitization processing, handles the time
For 320h, natural cooling cooling obtains presoma c；Presoma c is crushed, nodularization, classification, being crushed to D50 is 20um,
Wherein, nodularization time 35min is classified blower loading frequency 7HZ, grade frequency 35HZ, obtains presoma d；By presoma d and coal
Mixing in tar and glucose is that 85:15 mixes 1.5h at a temperature of 110 DEG C in mass ratio, obtains presoma e；By presoma
E is in helium atmosphere, Ventilation Rate 8L/min, 6 DEG C/min of heating rate, and sintering temperature is 1300 DEG C, 8h is sintered, to sintering
Material is sieved afterwards, obtains cathode material of lithium ion battery.
Specific embodiment 5
The preparation method of cathode material of lithium ion battery, comprising:
The raw ore coarse granule for being 72% by micro crystal graphite content, is placed in ball mill, after 350r/min ball milling 7h, is floated
Choosing, drying, magnetic separation, obtaining D50 is 5-100um, and carbon content throws micro crystal graphite powder in 90% or more micro crystal graphite powder
Enter volume ratio hydrofluoric acid: in hydrochloric acid=7:3 mix acid liquor, heating 65 DEG C, stir 3.5h, filter, much filtrate is washed with water, until
It washes out liquid PH and is greater than 4, much filtrate is filtered, is dried, obtain the presoma a that fixed carbon content is greater than 95%；By forerunner
Body a, binder, catalyst and auxiliary agent are that 70:25:12:6 is placed in ball mill according to mass ratio, wherein bonding agent is coal drip
Green, coal tar and polyacrylonitrile mixing；Catalyst is the mixing in silicon carbide and boron carbide, and catalyst grain size D50 is
5-30um, auxiliary agent are washing oil, are 28:72 by ratio of grinding media to material, after revolving speed 180r/min, ball milling mixing 4h, are with pressure by mixing
15MPa carries out briquetting, obtains presoma b；By presoma b in argon atmosphere, Ventilation Rate 9L/min, heating rate
4 DEG C/min, the low-temperature sintering that temperature is 500 DEG C is carried out, after being sintered 9h, the material of sintering is transferred to graphitizing furnace, is passed through nitrogen
Gas, Ventilation Rate 23L/min, 8 DEG C/min of heating rate, carrying out temperature is 3100 DEG C of high temperature graphitization processing, handles the time
For 310h, natural cooling cooling obtains presoma c；Presoma c is crushed, nodularization, classification, being crushed to D50 is 10um,
Wherein, nodularization time 28min is classified blower loading frequency 6HZ, grade frequency 36HZ, obtains presoma d；By presoma d and drip
The mixing of green and glucose mixes 1.8h at a temperature of 220 DEG C for 90:10 in mass ratio, obtains presoma e；By presoma e in argon
In gas atmosphere, Ventilation Rate 11L/min, 5 DEG C/min of heating rate, sintering temperature are 1100 DEG C, 12h are sintered, after sintering
Material is sieved, and cathode material of lithium ion battery is obtained.
The cathode material of lithium ion battery produced of embodiment 1 to 5, is applied on lithium ion battery, and purchase city
Negative electrode material on face applies in same lithium ion battery (comparative example 1 and comparative example 2), carries out to the battery of preparation
Charge-discharge test, the constant current charge-discharge under 0.1C multiplying power obtain the average charging capacity of each embodiment, discharge capacity and for the first time
Coulombic efficiency value is as a result as follows:
| Number | Charging capacity | Discharge capacity | Efficiency |
| Embodiment 1 | 355.32 | 382.96 | 92.78% |
| Embodiment 2 | 353.664 | 379.12 | 93.29% |
| Embodiment 3 | 357.538 | 383.42 | 93.25% |
| Embodiment 4 | 357.061 | 383.467 | 93.11% |
| Embodiment 5 | 356.324 | 381.32 | 93.44% |
| Comparative example 1 | 332.213 | 375.36 | 88.50% |
| Comparative example 2 | 328.452 | 369.78 | 88.82% |
According to the data in several tables, it can be seen that the cathode material of lithium ion battery of this preparation method preparation is applied to
In lithium ion battery, reversible capacity is big, and coulombic efficiency is high for the first time, and coulombic efficiency can achieve 93% or more, and stability for the first time
Good, consistency is excellent.
The cathode material of lithium ion battery of above method preparation, it is multiple by the compound second particle of carbon-coated micro crystal graphite
Condensation material porosity is 20%-80%, and aperture 1nm-1um, material particle size D50 are 5-25um, specific surface area 1-10m2/ g,
Tap density is 0.5-1.5g/cc, is orientated (I004/I110) less than 2.Cathode material of lithium ion battery according to figure 1
Scanning figure, it can be seen that micro crystal graphite outermost layer has coated amorphous carbon material, so that the coulombic efficiency for the first time of material mentions significantly
It rises；XRD x ray diffraction is carried out to cathode material of lithium ion battery, Fig. 2 can be seen that the negative electrode for lithium ion battery material of preparation
Material only has graphite crystal, no other impurities crystal (amorphous carbon material of cladding micro crystal graphite due to be it is noncrystal, and content compared with
Few, XRD, which spreads out, to be misfired).
A kind of lithium ion battery, including by negative electrode material, conductive agent (super P carbon black), sodium carboxymethylcellulose
(CMC), butadiene-styrene rubber (SBR): ratio of the deionized water according to mass ratio 85:5:5:5:100,1500r/min speed stirring 8h
Afterwards, it is coated on 10um thickness copper foil, coating thickness 50um obtains battery cathode sheet, Yi Jijin after roll-in, cutting, baking
Belong to lithium piece as positive electrode, electrolyte is selected as common lithium-ion battery electrolytes: 1.5mol/L lithium hexafluoro phosphate (LiPF6)/
Ethylene carbonate (EC): dimethyl carbonate (DMC): methyl ethyl carbonate (EMC) is the mixed liquor of 20:15:65.0.1C is carried out to it
Constant current charge-discharge test under multiplying power, referring to Fig. 3 as can be seen that its lower voltage limit 0.001V, upper limit voltage 2.0V.
The steps in the embodiment of the present invention can be sequentially adjusted, merged and deleted according to actual needs.
It is described in detail herein, applies specific case and the principle of the present invention and embodiment are explained
It states, above embodiments are merely used to help understand method and its core concept of the invention；Meanwhile for the general skill of this field
Art personnel, according to the thought of the present invention, there will be changes in the specific implementation manner and application range, in conclusion this
Description should not be construed as limiting the invention.
It is apparent to those skilled in the art that for convenience and simplicity of description, the system of foregoing description
It with the specific work process of unit, can refer to corresponding processes in the foregoing method embodiment, details are not described herein.
Claims (10)
1. a kind of preparation method of cathode material of lithium ion battery, which is characterized in that method includes:
S1. micro crystal graphite powder and acid-mixed are closed and carries out hot dipping processing, washed after hot dipping processing, obtain presoma a；
S2. by the presoma a and binder, catalyst and auxiliary agent ball milling mixing, briquetting is carried out, presoma b is obtained；
S3. the presoma b is sintered, then high temperature graphitization in protective atmosphere, obtains presoma c；
S4. the presoma c is crushed, nodularization, classification, obtains presoma d；
S5. by the presoma d and carbon source hot mixing, presoma e is obtained；
S6. by the presoma e under an inert atmosphere high temperature sintering, screening, obtain cathode material of lithium ion battery.
2. preparation method according to claim 1, which is characterized in that the S2 includes:
Presoma a, binder, catalyst and auxiliary agent are placed in ball milling according to mass ratio for 50-80:20-30:10-15:5-8
It is 20-30:70-80 by ratio of grinding media to material in machine, after ball milling mixing 2-8h, with pressure is that 10-25MPa carries out briquetting by mixing, obtains
Presoma b.
3. preparation method according to claim 2, which is characterized in that the bonding agent is coal tar pitch, coal tar, phenolic aldehyde tree
One of rouge, epoxy resin, polyacrylonitrile are a variety of；The catalyst is iron chloride, in silicon carbide, boron carbide, vanadium oxide
It is one or more, catalyst grain size D50 be 5-30um.
4. preparation method according to claim 1, which is characterized in that the micro crystal graphite powder is micro crystal graphite original ore powder
Chopping fine is ground, and the micro crystal graphite powder is low-carbon highly acidity micro crystal graphite powder, the low-carbon highly acidity microlite ink powder
The content of graphite of body is greater than 90%, and the micro crystal graphite raw ore content of graphite is 65-85%.
5. preparation method according to claim 1, which is characterized in that the S1 includes:
It is 5-100um, micro crystal graphite powder and volume ratio hydrofluoric acid of the carbon content greater than 90%: hydrochloric acid=7-9:1-3 by D50
It being mixed in mix acid liquor, wherein mix acid liquor and micro crystal graphite powder liquid consolidate mass ratio as 1.5-5:1, are heated to 45-75 DEG C,
2.5-3.5h is stirred, filters, much filtrate is washed with water, until washing out liquid PH is greater than 4, much filtrate is filtered, is dried, is obtained
Presoma a, wherein the fixed carbon content of presoma a is greater than 95%.
6. preparation method according to claim 1, which is characterized in that the S3 includes:
Presoma b is carried out to the low-temperature sintering that temperature is 100-600 DEG C in protective atmosphere, after being sintered 8-11h, by the object of sintering
It is 2500-3200 DEG C of high temperature graphitization processing that material, which carries out temperature, obtains presoma c；Wherein, the protective atmosphere is nitrogen or argon
One of gas is a variety of.
7. preparation method according to claim 1, which is characterized in that the S5 includes:
By presoma d and one of pitch, coal tar, phenolic resin, glucose or it is a variety of be in mass ratio 95-85:5-15
1.5-2.5h is mixed at a temperature of 110-280 DEG C, obtains presoma e.
8. preparation method according to claim 1, which is characterized in that the S6 includes:
By presoma e in one of nitrogen, argon gas and helium or a variety of atmosphere, sintering temperature is 750-1300 DEG C,
It is sintered 8-30h, material after sintering is sieved, cathode material of lithium ion battery is obtained.
9. a kind of cathode material of lithium ion battery, which is characterized in that the cathode material of lithium ion battery is by claim
Any preparation method of 1-8 is made.
10. a kind of lithium ion battery, which is characterized in that including the negative electrode material as made from claim 1-8 any preparation method,
Conductive agent, sodium carboxymethylcellulose, butadiene-styrene rubber, water coat the battery pole that copper foil is constituted according to mass ratio for 85:5:5:5:100
Piece constitutes lithium ion battery with opposing metallic lithium battery pole slice and electrolyte.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811358809.6A CN109346707A (en) | 2018-11-15 | 2018-11-15 | A kind of cathode material of lithium ion battery and preparation method thereof and lithium ion battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811358809.6A CN109346707A (en) | 2018-11-15 | 2018-11-15 | A kind of cathode material of lithium ion battery and preparation method thereof and lithium ion battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109346707A true CN109346707A (en) | 2019-02-15 |
Family
ID=65315230
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811358809.6A Withdrawn CN109346707A (en) | 2018-11-15 | 2018-11-15 | A kind of cathode material of lithium ion battery and preparation method thereof and lithium ion battery |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109346707A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109970052A (en) * | 2019-02-27 | 2019-07-05 | 福建翔丰华新能源材料有限公司 | A kind of method of natural graphite granulation and secondary coating modification |
| CN111463416A (en) * | 2020-04-14 | 2020-07-28 | 广东东岛新能源股份有限公司 | Low-cost low-expansion-rate long-circulation natural graphite-based composite material and preparation method and application thereof |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1851963A (en) * | 2006-05-19 | 2006-10-25 | 湛江市聚鑫电子材料有限公司 | Lithium-ion cell composite carbon negative polar material and preparing method |
| CN102148355A (en) * | 2011-03-03 | 2011-08-10 | 江西正拓新能源科技有限公司 | Cathode material for lithium-ion power battery and preparation method thereof |
| CN104591143A (en) * | 2013-10-30 | 2015-05-06 | 青岛泰浩达碳材料有限公司 | Purifying processing method for microcrystalline graphite |
| CN105977489A (en) * | 2016-03-22 | 2016-09-28 | 福建翔丰华新能源材料有限公司 | Preparation method of modified microcrystalline graphite anode material for lithium ion battery |
| CN106532044A (en) * | 2015-09-13 | 2017-03-22 | 上海杉杉科技有限公司 | Lithium secondary battery composite graphite and preparation method thereof |
| CN106532051A (en) * | 2015-09-29 | 2017-03-22 | 宁波杉杉新材料科技有限公司 | Method for preparing negative electrode material of power lithium-ion battery by using natural graphite |
| CN107732152A (en) * | 2017-10-31 | 2018-02-23 | 湖南国盛石墨科技有限公司 | A kind of micro crystal graphite negative electricity pole piece and its button lithium battery preparation method |
| CN107799770A (en) * | 2017-10-31 | 2018-03-13 | 湖南国盛石墨科技有限公司 | A kind of micro crystal graphite for lithium cell cathode material and preparation method thereof |
-
2018
- 2018-11-15 CN CN201811358809.6A patent/CN109346707A/en not_active Withdrawn
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1851963A (en) * | 2006-05-19 | 2006-10-25 | 湛江市聚鑫电子材料有限公司 | Lithium-ion cell composite carbon negative polar material and preparing method |
| CN102148355A (en) * | 2011-03-03 | 2011-08-10 | 江西正拓新能源科技有限公司 | Cathode material for lithium-ion power battery and preparation method thereof |
| CN104591143A (en) * | 2013-10-30 | 2015-05-06 | 青岛泰浩达碳材料有限公司 | Purifying processing method for microcrystalline graphite |
| CN106532044A (en) * | 2015-09-13 | 2017-03-22 | 上海杉杉科技有限公司 | Lithium secondary battery composite graphite and preparation method thereof |
| CN106532051A (en) * | 2015-09-29 | 2017-03-22 | 宁波杉杉新材料科技有限公司 | Method for preparing negative electrode material of power lithium-ion battery by using natural graphite |
| CN105977489A (en) * | 2016-03-22 | 2016-09-28 | 福建翔丰华新能源材料有限公司 | Preparation method of modified microcrystalline graphite anode material for lithium ion battery |
| CN107732152A (en) * | 2017-10-31 | 2018-02-23 | 湖南国盛石墨科技有限公司 | A kind of micro crystal graphite negative electricity pole piece and its button lithium battery preparation method |
| CN107799770A (en) * | 2017-10-31 | 2018-03-13 | 湖南国盛石墨科技有限公司 | A kind of micro crystal graphite for lithium cell cathode material and preparation method thereof |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109970052A (en) * | 2019-02-27 | 2019-07-05 | 福建翔丰华新能源材料有限公司 | A kind of method of natural graphite granulation and secondary coating modification |
| CN111463416A (en) * | 2020-04-14 | 2020-07-28 | 广东东岛新能源股份有限公司 | Low-cost low-expansion-rate long-circulation natural graphite-based composite material and preparation method and application thereof |
| CN111463416B (en) * | 2020-04-14 | 2021-09-07 | 广东东岛新能源股份有限公司 | Low-cost low-expansion-rate long-circulation natural graphite-based composite material and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103022462B (en) | Preparation method for high-conductivity lithium titanate cathode material of lithium battery | |
| CN105047892B (en) | Porous silica material, preparation method and application | |
| CN102394288B (en) | Silicon-carbon cathode material for lithium ion battery and manufacturing method thereof | |
| CN103214245B (en) | Carbon/carbon composite microsphere material, production method and lithium ion battery | |
| CN107507972A (en) | Preparation method, silicon-carbon cathode material and the lithium ion battery of silicon-carbon cathode material | |
| CN105098186A (en) | Pyrolysis amorphous carbon material and preparation method and application thereof | |
| CN108054357A (en) | Power lithium-ion battery coal base composite negative pole material and preparation method thereof | |
| CN109704323A (en) | Electrode material and secondary battery | |
| CN109817957B (en) | Preparation method of asphalt-coated silicon-doped natural crystalline flake graphite negative electrode material | |
| CN102280638A (en) | Vegetable protein carbon cladded nanometer lithium iron phosphate anode material and preparation method thereof | |
| CN108715447A (en) | A kind of camphor tree Quito mesoporous activated carbon and preparation method thereof and the application in electrochemical energy storage | |
| CN105789627A (en) | Preparation method of high-performance graphite negative electrode material for lithium ion battery | |
| CN109950520A (en) | A kind of nitrogenous graphene coated biomass carbon negative electrode material and preparation method thereof | |
| CN109449385A (en) | Carbon-coated unformed silicon/graphene composite negative pole and preparation method thereof and lithium ion battery | |
| CN104201343A (en) | Method for reducing specific surface area of spherical graphite | |
| CN106169582A (en) | A kind of natural pin Jiao's composite graphite negative electrode material production method | |
| CN109860559A (en) | Micro crystal graphite negative electrode material and preparation method, lithium ion battery | |
| CN109888181A (en) | A kind of carbon nitrogen lithium multiphase doped lithium ion battery negative electrode material and preparation method thereof and anode plate for lithium ionic cell and lithium ion battery | |
| CN105406071B (en) | A kind of high magnification vanadium phosphate cathode material and its preparation method and application | |
| CN105070889B (en) | A kind of preparation method, product and the application of the carbon fibre material of carried titanium dioxide nano thin-film and ferroferric oxide nano granules | |
| CN112736233A (en) | Lithium ion battery electrode active material, preparation method thereof, electrode and battery | |
| CN109065875A (en) | A kind of preparation method of the tertiary cathode material of Coated powder | |
| CN108615888A (en) | Lithium ion battery biomass carbon fiber negative material and its preparation method and application | |
| CN109346707A (en) | A kind of cathode material of lithium ion battery and preparation method thereof and lithium ion battery | |
| CN103311518B (en) | Hard-carbon negative electrode material for lithium ion secondary battery and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20200527 Address after: Room g0232, headquarters building, Changsha Zhongdian Software Park, No. 39, Jianshan Road, high tech Development Zone, Changsha City, Hunan Province Applicant after: Thornton New Energy Technology (Changsha) Co.,Ltd. Address before: 411100 Hunan province Xiangtan City Jiuhua Demonstration Zone No. 78 West Benz Applicant before: SOUNDON NEW ENERGY TECHNOLOGY Co.,Ltd. |
|
| TA01 | Transfer of patent application right | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WW01 | Invention patent application withdrawn after publication |
Application publication date: 20190215 |
|
| WW01 | Invention patent application withdrawn after publication |