CN109809386A - The method that ring-form calcining furnace is used for lithium cell cathode material carbonation process - Google Patents
The method that ring-form calcining furnace is used for lithium cell cathode material carbonation process Download PDFInfo
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- CN109809386A CN109809386A CN201910261919.9A CN201910261919A CN109809386A CN 109809386 A CN109809386 A CN 109809386A CN 201910261919 A CN201910261919 A CN 201910261919A CN 109809386 A CN109809386 A CN 109809386A
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- 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
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- 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 invention discloses a kind of methods for carrying out carbonization treatment to lithium cell cathode material using ring-form calcining furnace, belong to cell negative electrode material synthesis technical field.When the present invention is for cell negative electrode material is sintered using electric furnace in the prior art, energy consumption is big, it is at high cost, it is seriously polluted, the defects of production scale is limited, provide a kind of method that ring-form calcining furnace handles battery negative material carbonization, this method passes through hanging basket shove charge, and optimize temperature lift-down curve, solve many problems that ring-form calcining furnace preroast artificial graphite material raw product faces, product performance index is set to have reached electric sintering furnace Product Level, meet negative electrode material graphitization process requirement, it is high graphite cathode material carburizing sintering stepped cost has been broken, small scale, energy consumption is big, the big equal bottlenecks of environmental protection pressure.
Description
Technical field
The invention belongs to cell negative electrode material synthesis technical fields, and in particular to a kind of ring-form calcining furnace is to cathode of lithium battery
The method of material progress carbonization treatment.
Background technique
With the development of new energy technology, the development of lithium ion battery industry be also advance by leaps and bounds as at present it is most ideal,
The advantages such as most practical lithium cell cathode material, artificial graphite is good with its stability, good conductivity, and cyclicity is good occupy lithium battery
Negative electrode material market overwhelming majority share.
In the production technology of artificial graphite, the pre-sintering carbonization to graphite raw product is to advance in graphitization process
One step reduces the content of volatile matter in material, further increases the carbon containing percentage of material, and reduce graphitization process to environment
Pollution.Graphitization producer largely uses the sintering process of electric furnace completion product at present, but traditional electric furnace energy consumption is big, maintenance cost
Height also needs secondary treatment after generated fume collection, and production scale is limited.
Summary of the invention
When the present invention is for carbonization treatment is carried out to lithium cell cathode material using electric furnace in the prior art, energy consumption is big, at
This height, seriously polluted, the defects of production scale is limited, provide a kind of ring-form calcining furnace for lithium cell cathode material carbonizer
The method of sequence, this method include shove charge and roasting,
The shove charge operation are as follows: the raw material of carbonization treatment will be needed to be packed into steel hanging basket, then hanging basket is put into ring type roasting
It burns in furnace furnace chamber, hole fills coke granule to completely cut off air around steel basket；
The baking operation are as follows: by heating and cooling process of the following state modulator in roaster:
。
Wherein, ring-form calcining furnace described above is in the method for lithium cell cathode material carbonation process, shove charge to be operated
In, the size of the steel hanging basket is more bigger than product, and than furnace chamber undersized, surrounding is aided with the coke filling of 0~6mm diameter again
Material.
Preferably, ring-form calcining furnace described above is in the method for lithium cell cathode material carbonation process, roasting to be grasped
In work, by heating and cooling process of the following state modulator in roaster:
| Go up and down thermophase | Phase temperature (DEG C) | Warming and cooling rate (DEG C/h) |
| Warm-up phase | 50 rise to 300 ± 20 | 10~15 |
| Temperature rise period | 300 ± 20 rise to 600 ± 20 | 5~10 |
| Low-temperature bake | 600 ± 20 rise to 850 ± 20 | 8~10 |
| Medium temperature roast | 850 ± 20 rise to 1080 ± 20 | 8~10 |
| High-temperature roasting | 1080±20 | Keep the temperature 30 ± 2h |
| One-step cooling | 1080 ± 20 are down to 800 ± 20 | 10~15 |
| Two-step cooling | 800 ± 20 are down to 300 | 25 |
。
The beneficial effects of the present invention are:
Providing for the invention a kind of is carbonized to lithium cell cathode material using open-type ring-type roasting furnace
The technique of processing, optimizes charging method, and accurately controls to the heating and cooling parameter of firing stage, explored compared with
Excellent temperature lift-down curve meets negative electrode material index and wants so that product performance index be enable to reach electric sintering furnace Product Level
It asks；The method of the present invention uses natural gas as heat energy source, and cost substantially reduces, and asphalt volatile constituents can further burn, and generates water
And carbon dioxide, fuel cost, but also safety and environmental protection are not only reduced, and production capacity greatly improved, is worthy of popularization.
Detailed description of the invention
Fig. 1 is barrel structure of the present invention and charging schematic diagram.
Specific embodiment
It is carbonized using open-type ring-type roasting furnace to lithium cell cathode material, relative to electric stove for following advantage:
First using natural gas as heat energy source, cost is substantially reduced, and second generated asphalt volatile constituents can further burn,
Water and carbon dioxide are generated, not only reduces fuel cost, but also safety and environmental protection, and production capacity greatly improved.
Graphite product raw materials for production are mainly coke and the pitch as binder, product formula, granularity and required roasting
Final temperature is entirely different with prebaked anode for aluminium electrolysis, if not changing roasting technique, is directly produced, be will lead to ring-form calcining furnace
Product generates a large amount of crackles, and the important parameters such as coking value, real density, electric conductivity are unable to satisfy properties of product requirement；Due to ring
Formula furnace different parts temperature differs greatly, and also results in product and integrally heats up unevenly, and the product quality and performances of firing are uneven
It is even.Inventor carries out carbonization processing to can be realized ring-form calcining furnace to lithium cell cathode material, has carried out a large amount of creativeness
The bottlenecks such as labour, it is at high cost to have broken graphite cathode material sintering stage, small scale, and energy consumption is big, environmental protection pressure is big.
Specifically, the method that ring-form calcining furnace is used for lithium cell cathode material carbonation process, this method includes shove charge and roasting
It burns,
The shove charge operation are as follows: the raw material of carbonization treatment will be needed to be packed into steel hanging basket, then hanging basket is put into ring type roasting
It burns in furnace furnace chamber, hole fills coke granule to completely cut off air around steel basket；
The baking operation are as follows: by heating and cooling process of the following state modulator in roaster:
。
Since raw product Asphalt Content is big, volatile content is high and raw material is powder material, to avoid firing just
Softening transform occurs for the phase, first in loading furnace process, the loading of product is used for using steel hanging basket, steel column size to be omited than product
Greatly, than furnace chamber undersized, after hanging basket is put into roaster, surrounding is aided with the coke fillers of 0~6mm diameter again, make product with
Air exclusion comes, and product is avoided to aoxidize, while playing the role of thermally conductive and supporting steel basket geometry (such as Fig. 1 institute
Show).
The present invention needs strict control during roasting furnace temperature elevation, to different temperatures stage warming and cooling rate, using " two
Head is fast, intermediate slow " principle, the stage is discharged in especially asphalt volatile constituents, and heating rate slowly will keep heating inside product equal
Even, fugitive constituent is sufficiently discharged, and improves coking value, otherwise product can be made to crack, while article construction is loose, and porosity is big,
Influence the final performance of product；The stage of reaching a high temperature will keep certain time, further increase every physicochemical property of product.
In order to make product performance index reach electric sintering furnace Product Level, meets negative electrode material graphitization process requirement, pass through
It crosses and repeatedly practises, explored optimal temperature lift-down curve:
。
The performance analysis of the method for the present invention: it if produced using electric furnace, is calculated by monthly 1000 tons of yield, required consumption electric energy
1200 KWhs/ton, if produced using circular furnace, 90 sides of required consumption natural gas/ton；0.35 yuan of electricity price/degree, 2.3 yuan of natural gas/
Side；Steel basket can burn 30 tons of products by 1 ton of steel and calculate, and cost is at 150,000 yuan；It then can monthly save about 1000*
Ten thousand yuan of (1200*0.35-90*2.3) -150000=6.3,75.6 ten thousand yuan of annual escapable cost, while saving
Environmentally friendly cost.
It is described further below by way of example forms, but the range that this should not be interpreted as to the above-mentioned theme of the present invention only limits
In following instance, the techniques implemented on the basis of the foregoing are all within the scope of the present invention.
Embodiment 1
The raw material of carbonization treatment will be needed to be packed into steel hanging basket, overhead traveling crane is reused by hanging basket and be put into ring-form calcining furnace furnace chamber
In, hole fills coke granule to completely cut off air around steel basket；
By heating and cooling process of 1 state modulator of table in roaster:
1 embodiment of table, 1 temperature lift-down curve
| Go up and down thermophase | Phase temperature (DEG C) | Warming and cooling rate (DEG C/h) |
| Warm-up phase | 50 rise to 300 ± 20 | 10~15 |
| Temperature rise period | 300 ± 20 rise to 600 ± 20 | 10~15 |
| Low-temperature bake | 600 ± 20 rise to 850 ± 20 | 5~10 |
| Medium temperature roast | 850 ± 20 rise to 980 ± 20 | 8~10 |
| High-temperature roasting | 980±20 | Keep the temperature 20h |
| One-step cooling | 980 ± 20 are down to 800 ± 20 | 20 |
| Two-step cooling | 800 ± 20 are down to 300 | 25 |
The product index fired using above-mentioned shove charge and temperature lift-down curve is as described in Table 2:
2 embodiment of table, 1 product index
| Compression strength (MPa) | Resistivity (μ Ω .m) | Real density (g/cm3) | Bulk density (g/cm3) |
| 30 | 60 | 2.03 | 1.07 |
Compression strength is lower, and resistivity is higher.
Embodiment 2
The raw material of carbonization treatment will be needed to be packed into steel hanging basket, overhead traveling crane is reused by hanging basket and be put into ring-form calcining furnace furnace chamber
In, hole fills coke granule to completely cut off air around steel basket；
In order to reduce resistivity, the present embodiment further increases product roasting final temperature, while extending soaking time, by table 3
Temperature-rise period of the state modulator in roaster:
3 embodiment of table, 2 temperature lift-down curve
| Go up and down thermophase | Phase temperature (DEG C) | Warming and cooling rate (DEG C/h) |
| Warm-up phase | 50 rise to 300 ± 20 | 10~15 |
| Temperature rise period | 300 ± 20 rise to 600 ± 20 | 10~15 |
| Low-temperature bake | 600 ± 20 rise to 850 ± 20 | 5~10 |
| Medium temperature roast | 850 ± 20 rise to 1080 ± 20 | 8~10 |
| High-temperature roasting | 1080±20 | Keep the temperature 30h |
| One-step cooling | 1080 ± 20 are down to 800 ± 20 | 20 |
| Two-step cooling | 800 ± 20 are down to 300 | 25 |
The product index fired using above-mentioned shove charge and temperature lift-down curve is as described in Table 4:
4 embodiment of table, 2 product index
| Compression strength (MPa) | Resistivity (μ Ω .m) | Real density (g/cm3) | Bulk density (g/cm3) |
| 28 | 57 | 2.05 | 1.05 |
After temperature adjustment, resistivity and real density, which have, to be obviously improved, but small product size density and compression strength have instead
A little to reduce, product crackle rejection rate is more.
Analyzing reason is that the rising of temperature rise period temperature is too fast, causes the product fugitive constituent velocity of discharge too fast, the porosity increases.
The fast Producing reason of crackle with heating rate except having outside the Pass, and the unbalanced influence of temperature is also larger, because of roaster hopper
Position is different, and temperature difference is larger, and furnace chamber edge hopper and middle material case temperature difference reach 80 DEG C or so, causes product heated not
Equilibrium, product easily crack, and it requires that graphite product is placed on position hopper among furnace chamber, the hopper close to edge
For firing other products.
Embodiment 3
The raw material of carbonization treatment will be needed to be packed into steel hanging basket, overhead traveling crane is reused by hanging basket and be put into ring-form calcining furnace furnace chamber
In, hole fills coke granule to completely cut off air around steel basket；
Embodiment 3 readjusts temperature curve, while suitably reducing cooling velocity, by 5 state modulator of table in roaster
Heating and cooling process:
5 embodiment of table, 3 temperature lift-down curve
The product index fired using above-mentioned shove charge and temperature lift-down curve is as described in Table 6:
6 embodiment of table, 3 product index
| Compression strength (MPa) | Resistivity (μ Ω .m) | Real density (g/cm3) | Bulk density (g/cm3) |
| 33 | 56 | 2.07 | 1.15 |
Product performance index has reached electric sintering furnace Product Level, meets graphite cathode material carbonation process requirement.
Steel column is taken out with multifunction crane after the completion of firing, product can enter next process graphite after cooling
Change, steel column repairs reusable on inspection.
By Examples 1 to 3 it is found that the present invention has found a set of optimal temperature lift-down curve, solve ring by repeatedly practising
Many problems that formula roaster preroast artificial graphite material raw product faces, make product performance index reach electric sintering furnace production
Product are horizontal, meet negative electrode material graphitization process requirement, broken graphite cathode material carburizing sintering stepped cost height, scale
It is small, the bottlenecks such as energy consumption is big, environmental protection pressure is big.
Claims (3)
1. the method that ring-form calcining furnace is used for lithium cell cathode material carbonation process, including shove charge and roasting, it is characterised in that:
The shove charge operation are as follows: the raw material of carbonization treatment will be needed to be packed into steel hanging basket, then hanging basket is put into ring-form calcining furnace
In furnace chamber, hole fills coke granule to completely cut off air around steel basket；
The baking operation are as follows: by heating and cooling process of the following state modulator in roaster:
。
2. the method that ring-form calcining furnace according to claim 1 is used for lithium cell cathode material carbonation process, feature exist
In: in shove charge operation, the size of the steel hanging basket is more bigger than product, and than furnace chamber undersized, it is straight that surrounding is aided with 0~6mm again
The coke fillers of diameter.
3. the method that ring-form calcining furnace according to claim 1 or 2 is used for lithium cell cathode material carbonation process, feature
It is: in baking operation, by heating and cooling process of the following state modulator in roaster:
。
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112629247A (en) * | 2020-12-21 | 2021-04-09 | 苏州科尔珀恩机械科技有限公司 | Lithium battery negative electrode material roasting furnace and roasting method |
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