CN109192924A - A kind of method of carbon encapsulated material destressing and residual carbon - Google Patents
A kind of method of carbon encapsulated material destressing and residual carbon Download PDFInfo
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- CN109192924A CN109192924A CN201811156942.3A CN201811156942A CN109192924A CN 109192924 A CN109192924 A CN 109192924A CN 201811156942 A CN201811156942 A CN 201811156942A CN 109192924 A CN109192924 A CN 109192924A
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- 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
- H01M4/04—Processes of manufacture in general
- H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
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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
- 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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Abstract
A kind of method of carbon encapsulated material destressing and residual carbon, carbon-coated material will have been completed by, which being handled by low-temperature annealing, is placed in T DEG C of isothermal holding of progress in sintering furnace, sintering furnace is warming up to T DEG C with the rate of 6 DEG C/min, and about T DEG C fluctuation is within 50 DEG C, soaking time is t hours, cool down after heat preservation, rate of temperature fall is controlled in 3 DEG C/min, it is cooled to≤80 DEG C, after discharge, protective gas and oxygen are passed through in heat preservation and temperature-fall period, the purity of the protective gas is 99.99%, oxygen flux control in protection air-flow amount 1/200 ~ 1/100, make in sintering furnace oxygen content in 200-1000ppm, the oxygen treatments applied time is the 1/10-1/5 of total soaking time, the present invention is using control gas flow, the stream of component and material Dynamic property, is removed surplus carbon and destressing, reduces fault in material.
Description
Technical field
The present invention relates to technical field of smelting, the particularly a kind of method of carbon encapsulated material destressing and residual carbon.
Background technique
After battery assembly in charge and discharge process, contact due to electrolyte with positive and negative anodes can cause positive and negative pole material knot
Structure collapses, and influences the cycle performance of battery.The method used in industry mainly realized by carbon coating positive and negative pole material with
Contact of electrolyte, such as LiFePO4, lithium titanate etc., one side carbon coating can reduce connecing for positive and negative pole material and electrolyte
Side reaction is touched, the conductivity of material is on the other hand improved.In addition, there are also silicon carbon materials etc. to inhibit silicon using means such as carbon coatings
Expansion, carbon coating is the modified excellent means of many positive and negative pole materials.
At the same time, carbon coating existing defects, such as during heat treatment due to needing the synthesis of comprehensive positive electrode,
Treatment temperature is unsuitable excessively high and too long, in order to avoid cause the burning of positive electrode.This results in cladding that can introduce excessive carbon source guarantor
Demonstrate,prove the uniformity and integrality of cladding.It can bring about the dendrite or residual carbon of carbon coating layer in this way.
Elimination residual carbon is mentioned in a kind of method (authorization publication No.: CN1210204C) for preparing silicon carbide of Chinese patent
Means differed greatly using the method for heating removal in 800 DEG C or less air with the method in this patent, this method only
Energy use should not be denaturalized in silicon carbon material, and in air, low to atmosphere requirements.General carbon-coated material is in such work
It can fail under the conditions of skill.This patent breaches such boundary.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of method of carbon encapsulated material destressing and residual carbon.
A kind of method of carbon encapsulated material destressing and residual carbon, specific preparation process are as follows:
S1: it low-temperature annealing processing: will complete to carry out T DEG C of isothermal holding, sintering furnace in carbon-coated material merging sintering furnace
It is warming up to T DEG C with the rate of 6 DEG C/min, and about T DEG C fluctuation, within 50 DEG C, soaking time is t hours,
When T≤200 DEG C, t=K (K is fixed constant, 2≤K≤24),
When 200 DEG C of T >, t=K- (T-200) * n n=(T-200)/200；
S2: cooling down after heat preservation, rate of temperature fall control in 3 DEG C/min, be cooled to≤80 DEG C, after discharge, keep the temperature
Be passed through protective gas and oxygen in temperature-fall period, the purity of the protective gas is 99.99%, and sintering furnace is arranged six altogether
Air inlet is arranged three in furnace body two sides respectively, and either side is equipped with an oxygen port and two protection ports, oxygen port are being protected
It among port, is arranged in parallel, pressure is less than protection gas, and oxygen flux control makes to be sintered the 1/200 ~ 1/100 of protection air-flow amount
For oxygen content in 200-1000ppm, the oxygen treatments applied time is the 1/10-1/5 of total soaking time in furnace.
Further, described completed in carbon-coated material merging sintering furnace by the way of spiral charging, material
Vent is arranged in discharging end in material, and exhaust outlet is 6 times for protecting port bore, and flapper valve is arranged in exhaust outlet, according to
The size of the size control gas outlet valve of charge flow rate, carries out cyclone collection to the particle in charging, charging rate and is passed through
The gas flow of the protective gas of sintering furnace is positively correlated, its calculation formula is:
L=aV/10+0.55(a is correction constant, range: 0.3 < a < 1.0)
Wherein V is charging rate, and unit Wei ㎏/h, L are the gas flow of protective gas, unit m3/h.
Further, described T DEG C is determined according to the carbon-coated structure of material surface and the property of itself, positive electrode institute
T DEG C of range of setting is 200 DEG C ~ 350 DEG C, and T DEG C of range set by negative electrode material is 300 DEG C ~ 600 DEG C.
Further, the protective gas is nitrogen, argon gas, the one or more of the inert gases such as helium.
The invention has the benefit that
By remove residual carbon method, from material in nature, the specific surface area 1-2m of material can be reduced2/ g reduces material
The pH value 0.3-1 of material, and other electrical property frees of losses, in addition, since the elimination of surface residual carbon (can pass through SEM picture pair
Than), low-surface-energy is dropped, plays the role of spheroidized particle indirectly, the pulping process of battery plus-negative plate material can be played good
Facilitation reinforces the dispersion of each active material.
Detailed description of the invention
Fig. 1 is LiFePO4 LiFePO4SEM picture before the destressing of carbon encapsulated material；
Fig. 2 is LiFePO4 LiFePO4SEM picture after the destressing of carbon encapsulated material.
Specific embodiment
Invention is further explained with specific embodiment for explanation with reference to the accompanying drawing.
A kind of method of carbon encapsulated material destressing and residual carbon, specific preparation process are as follows:
S1: it low-temperature annealing processing: will complete to carry out T DEG C of isothermal holding, sintering furnace in carbon-coated material merging sintering furnace
It is warming up to T DEG C with the rate of 6 DEG C/min, and about T DEG C fluctuation, within 50 DEG C, soaking time is t hours,
When T≤200 DEG C, t=K (K is fixed constant, 2≤K≤24),
When 200 DEG C of T >, t=K- (T-200) * n n=(T-200)/200；
S2: cooling down after heat preservation, rate of temperature fall control in 3 DEG C/min, be cooled to≤80 DEG C, after discharge, keep the temperature
Be passed through protective gas and oxygen in temperature-fall period, the purity of the protective gas is 99.99%, and sintering furnace is arranged six altogether
Air inlet is arranged three in furnace body two sides respectively, and either side is equipped with an oxygen port and two protection ports, oxygen port are being protected
It among port, is arranged in parallel, pressure is less than protection gas, and oxygen flux control makes to be sintered the 1/200 ~ 1/100 of protection air-flow amount
For oxygen content in 200-1000ppm, the oxygen treatments applied time is the 1/10-1/5 of total soaking time in furnace.
Further, described completed in carbon-coated material merging sintering furnace by the way of spiral charging, material
Vent is arranged in discharging end in material, and exhaust outlet is 6 times for protecting port bore, and flapper valve is arranged in exhaust outlet, according to
The size of the size control gas outlet valve of charge flow rate, carries out cyclone collection to the particle in charging, charging rate and is passed through
The gas flow of the protective gas of sintering furnace is positively correlated, its calculation formula is:
L=aV/10+0.55(a is correction constant, range: 0.3 < a < 1.0)
Wherein V is charging rate, and unit Wei ㎏/h, L are the gas flow of protective gas, unit m3/h.
Further, described T DEG C is determined according to the carbon-coated structure of material surface and the property of itself, positive electrode institute
T DEG C of range of setting is 200 DEG C ~ 350 DEG C, and T DEG C of range set by negative electrode material is 300 DEG C ~ 600 DEG C.
Further, the protective gas is nitrogen, argon gas, the one or more of the inert gases such as helium.
Embodiment 1
Carbon-coated 200 DEG C of LiFePO 4 material progress of isothermal holding will have been completed first, and soaking time was burnt at 2 hours
The rate of temperature fall of freezing of a furnace controls the rate of temperature fall after 6 DEG C/min, heat preservation and controls in 3 DEG C/min, in heat preservation and temperature-fall period
In need logical protective gas, the ingredient of protective gas is the nitrogen that purity is 99.99%, guarantee in furnace oxygen content in 500ppm,
The oxygen treatments applied time is 30min, is entered in sintering furnace by the way of spiral charging in material, 160 ㎏ of charging rate/h is gentle
Body flow 5.5m3/ h, exhaust outlet control valve to 1/6 open wide, and carry out cyclone collection, material drop temperature to the particle in charging
Control is at 80 DEG C.
Embodiment 2
Carbon-coated 300 DEG C of lithium titanate material progress of isothermal holding will have been completed first, and soaking time was at 5 hours, sintering
The rate of temperature fall of furnace controls the rate of temperature fall after 6 DEG C/min, heat preservation and controls in 3 DEG C/min, in heat preservation and temperature-fall period
Need logical protective gas, the ingredient of protective gas is the nitrogen that purity is 99.99%, guarantee in furnace oxygen content in 1000ppm,
Time 60min is handled, material enters in sintering furnace by the way of spiral charging, 200 ㎏ of charging rate/h and gas flow
9.05m3/ h, exhaust outlet control valve to 1/4 open wide, and carry out cyclone collection, the control of material drop temperature to the particle in charging
At 50 DEG C.
Embodiment 3
The isothermal holding that carbon-coated silicon carbon material carries out 400 DEG C will be completed first, soaking time was at 8 hours, sintering furnace
Rate of temperature fall control the rate of temperature fall control after 6 DEG C/min, heat preservation and needed in heat preservation and temperature-fall period in 3 DEG C/min
Lead to protective gas, the ingredient of protective gas is the nitrogen that purity is 99.99%, guarantees that oxygen content is at 1000ppm, place in furnace
Time 120min is managed, material enters in sintering furnace by the way of spiral charging, 120 ㎏ of charging rate/h and gas flow
9.55m3/ h, exhaust outlet control valve to 1/4 open wide, and carry out cyclone collection, the control of material drop temperature to the particle in charging
At 40 DEG C.
Claims (4)
1. a kind of method of carbon encapsulated material destressing and residual carbon, specific preparation process is as follows:
S1: it low-temperature annealing processing: will complete to carry out T DEG C of isothermal holding, sintering furnace in carbon-coated material merging sintering furnace
It is warming up to T DEG C with the rate of 6 DEG C/min, and about T DEG C fluctuation, within 50 DEG C, soaking time is t hours,
When T≤200 DEG C, t=K (K is fixed constant, 2≤K≤24),
When 200 DEG C of T >, t=K- (T-200) * n n=(T-200)/200；
S2: cooling down after heat preservation, rate of temperature fall control in 3 DEG C/min, be cooled to≤80 DEG C, after discharge, keep the temperature
Be passed through protective gas and oxygen in temperature-fall period, the purity of the protective gas is 99.99%, and oxygen flux control is being protected
The 1/200 ~ 1/100 of throughput is protected, makes in sintering furnace oxygen content in 200-1000ppm, when the oxygen treatments applied time is total heat preservation
Between 1/10-1/5.
2. a kind of method of carbon encapsulated material destressing and residual carbon according to claim 1, which is characterized in that it is described
It completes in carbon-coated material merging sintering furnace by the way of spiral charging, vent is arranged in discharging end in material,
Cyclone collection is carried out to the particle in charging, charging rate and the gas flow for the protective gas for being passed through sintering furnace are positively correlated,
Calculation formula are as follows:
L=aV/10+0.55(a is correction constant, range: 0.3 < a < 1.0)
Wherein V is charging rate, and unit Wei ㎏/h, L are the gas flow of protective gas, unit m3/h.
3. a kind of method of carbon encapsulated material destressing and residual carbon according to claim 1, which is characterized in that described T DEG C
It is to be determined according to the carbon-coated structure of material surface and the property of itself, T DEG C of range set by positive electrode is 200 DEG C ~
350 DEG C, T DEG C of range set by negative electrode material is 300 DEG C ~ 600 DEG C.
4. a kind of method of carbon encapsulated material destressing and residual carbon according to claim 1, which is characterized in that the protection
Gas is nitrogen, argon gas, the one or more of the inert gases such as helium.
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| CN201811156942.3A CN109192924A (en) | 2018-09-30 | 2018-09-30 | A kind of method of carbon encapsulated material destressing and residual carbon |
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| CN201811156942.3A CN109192924A (en) | 2018-09-30 | 2018-09-30 | A kind of method of carbon encapsulated material destressing and residual carbon |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101931073A (en) * | 2009-06-23 | 2010-12-29 | 中国科学院化学研究所 | Preparation method of lithium iron phosphate/carbon composite cathode material |
| CN102496720A (en) * | 2011-12-16 | 2012-06-13 | 重庆市科学技术研究院 | Method for preparing carbon-coated cathode material lithium vanadium phosphate |
| CN102651475A (en) * | 2012-05-28 | 2012-08-29 | 深圳市贝特瑞新能源材料股份有限公司 | Synthesizing method of anode material lithium iron phosphate of lithium ion battery |
| CN108475813A (en) * | 2016-01-06 | 2018-08-31 | 株式会社村田制作所 | Non-aqueous secondary batteries, positive active material and its manufacturing method for non-aqueous secondary batteries |
-
2018
- 2018-09-30 CN CN201811156942.3A patent/CN109192924A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101931073A (en) * | 2009-06-23 | 2010-12-29 | 中国科学院化学研究所 | Preparation method of lithium iron phosphate/carbon composite cathode material |
| CN102496720A (en) * | 2011-12-16 | 2012-06-13 | 重庆市科学技术研究院 | Method for preparing carbon-coated cathode material lithium vanadium phosphate |
| CN102651475A (en) * | 2012-05-28 | 2012-08-29 | 深圳市贝特瑞新能源材料股份有限公司 | Synthesizing method of anode material lithium iron phosphate of lithium ion battery |
| CN108475813A (en) * | 2016-01-06 | 2018-08-31 | 株式会社村田制作所 | Non-aqueous secondary batteries, positive active material and its manufacturing method for non-aqueous secondary batteries |
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Application publication date: 20190111 |
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