CN107482187A - Pitch carbon coating fluorocarbons positive electrode and preparation method thereof - Google Patents
Pitch carbon coating fluorocarbons positive electrode and preparation method thereof Download PDFInfo
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- CN107482187A CN107482187A CN201710621698.2A CN201710621698A CN107482187A CN 107482187 A CN107482187 A CN 107482187A CN 201710621698 A CN201710621698 A CN 201710621698A CN 107482187 A CN107482187 A CN 107482187A
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- fluorocarbons
- pitch
- preparation
- positive electrode
- carbon coating
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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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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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
- H01M4/36—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
- H01M4/5835—Comprising fluorine or fluoride salts
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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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
- H01M6/00—Primary cells; Manufacture thereof
- H01M6/14—Cells with non-aqueous electrolyte
- H01M6/16—Cells with non-aqueous electrolyte with organic electrolyte
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- General Chemical & Material Sciences (AREA)
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- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a kind of pitch carbon coating fluorocarbons positive electrode and preparation method thereof, preparation method is：Fluorocarbons is mixed with pitch, is sieved after heat treated and the fluorocarbons positive electrode of pitch carbon coating is made.This method uses pitch carbon coating fluorocarbons, by improving the adhesion between fluorination carbon surface and carbon source, the electric conductivity of material is improved to a greater degree, so as to significantly improve its discharge voltage plateau, specific capacity and heavy-current discharge performance.This method has the advantages that cost is low, equipment is simple, process conditions are simple and easy to control, yield is high, is very suitable for scale industrial production.
Description
Technical field
The invention belongs to lithium primary battery field of material technology, more particularly to a kind of pitch carbon coating fluorocarbons positive pole material
Material and preparation method thereof.
Background technology
Fluorocarbons has specific capacity high as lithium primary battery positive electrode, use temperature range is wide, operating voltage is high,
The advantages that resting period is long, it has also become the hot research material of substitution manganese dioxide positive pole material.However, C-F keys in fluorocarbons
Exist in the form of covalent bond, cause that its conductance is extremely low, and high rate performance is poor, discharge process heat production is serious, and it is extensive to limit its
Using.Therefore, people are directed to carrying out mixing modification or coating modification to fluorocarbons to improve the electric conductivity of material, solve fluorine
Changing carbon high rate performance difference etc. need to urgently solve the problems, such as.
CN201310478262.4 and CN201610208047.6, which is individually disclosed, utilizes Nanometer Copper and Nano semiconductor pair
Fluorocarbons carries out mixing modification, and CN201110431480.3 and CN201510641793.X are individually disclosed by polyaniline and gathered
Pyrroles carries out coating modification to fluorocarbons.Although the above method improves the electric conductivity of fluorinated carbon material and forthright again in various degree
Can, but weak point is individually present.Mixing modification method, which exists, blends the problem of uneven, and coating modification has organic solvent ring
Border pollution problem, and both modification dosage of addition are more, all exist and exchange high rate capability for sacrifice fluorocarbons specific capacity
Situation.
The content of the invention
In order to solve the above-mentioned technical problem, the present invention provides a kind of pitch carbon coating fluorocarbons positive electrode and its preparation side
The advantages of method, the pitch carbon coating fluorocarbons positive electrode have specific capacity height, multiplying power height, and cost is low, preparation method is easy to
Operation, suitable for large-scale production.
Therefore, technical scheme is as follows：
A kind of pitch carbon coating fluorocarbons positive electrode, the quality of the surface coated bitumencarb of fluorocarbons account for the matter of fluorocarbons
Measure percentage≤15%.
A kind of preparation method of pitch carbon coating fluorocarbons positive electrode, comprises the following steps：
1) fluorocarbons is well mixed with pitch, obtains material I；
2) the material I is heat-treated under atmosphere of inert gases protection, then through cooling down, sieving to obtain the pitch-coating
Fluorocarbons positive electrode.
Further, the carbonaceous amount in step 1) in pitch accounts for percentage≤15% of fluorocarbons quality.
Carbonaceous amount in pitch refers to：Pitch is handled into 1h under 500 DEG C, nitrogen atmosphere, obtains the quality of product (in file
The quality for the bitumencarb that other places are mentioned is also to be measured with same procedure).
Further, the condition of step 2) heat treatment is that 0.5~10h is handled under the conditions of 300~550 DEG C.
Further, the inert gas is argon gas or nitrogen.
Further, the fluorocarbons is fluorographite, fluorination coke, fluorination carbon black, carbon fluoride nano-tube and fluorographite
Any one in alkene or any several mixtures with any ratio.
Further, the pitch for asphalt, coal tar pitch and bitumen any one or it is any several with any
The mixture of ratio.
The selection of technical scheme bitumencarb is as cladding carbon source, it is therefore an objective to low with surface energy using the low pitch of surface energy
Fluorocarbons is combined, and improves the interface binding power of carbon coated and fluorocarbons, improves the carbon coating effect of fluorination carbon surface, so as to pole
The big high rate performance for improving fluorocarbons.Using less amount of pitch carbon coating fluorocarbons, you can reach preferable fluorinated carbon material
Multiplying power improvement, overcome to sacrifice the FAQs that fluorocarbons specific capacity exchanges high rate capability for.
The preparation method device therefor is simple, easily operated, process conditions are simple and easy to control, is suitable for large-scale production；Most
Not only specific capacity is high, multiplying power is high but also discharge voltage plateau is obviously improved for pitch carbon coating fluorocarbons positive electrode made from end,
Voltage delay phenomenon is obviously improved, and can meet the requirement of practical application.
Brief description of the drawings
Fig. 1 is that assembling product battery 0.1C discharge performances made from each embodiment, comparative example are compared into figure；
Fig. 2 is that assembling product battery 1C discharge performances made from each embodiment, comparative example are compared into figure；
Embodiment
Technical scheme is described in detail below in conjunction with drawings and examples.
Embodiment 1
Account for fluorocarbons quality according to the carbonaceous amount in pitch 1% weighs pitch, fluorocarbons, and both are mixed, then 500
DEG C, be heat-treated 2h under nitrogen atmosphere；Cooling, sieving, obtain pitch carbon coating fluorocarbons positive electrode.
Electric discharge of the pitch carbon coating fluorocarbons positive electrode that test the present embodiment obtains in 2032 type button cells
Energy；
Electrode material forms：The weight of pitch carbon coating fluorocarbons positive electrode and conductive agent SP and binding agent PVDF
Than for 90:5:5；It is lithium metal to electrode；Electrolyte is 1mol/L LiPF6EC/DMC (volume ratios 1:1) solution；Barrier film
For the micro-pore septums of Cellgard 2400.The current density of battery testing is 0.1C and 1C, and discharge voltage range is 3~1.5V.
Embodiment 2
Account for fluorocarbons quality according to the carbonaceous amount in pitch 5% weighs pitch, fluorocarbons, and both are mixed, then 400
DEG C, be heat-treated 5h under argon gas atmosphere；Cooling, sieving, obtain pitch carbon coating fluorocarbons positive electrode.
The pitch carbon coating fluorocarbons positive electrode that the present embodiment obtains is tested according to method in embodiment 1 to buckle in 2032 types
Discharge performance in formula battery.
Embodiment 3
Account for fluorocarbons quality according to the carbonaceous amount in pitch 2% weighs pitch, fluorocarbons, and both are mixed, then 400
DEG C, be heat-treated 8h under nitrogen atmosphere；Cooling, sieving, obtain pitch carbon coating fluorocarbons positive electrode.
The pitch carbon coating fluorocarbons positive electrode that the present embodiment obtains is tested according to method in embodiment 1 to buckle in 2032 types
Discharge performance in formula battery.
Comparative example 1
Test discharge performance of the fluorocarbons in 2032 type button cells：
Electrode material forms：Fluorocarbons positive electrode and conductive agent SP and binding agent PVDF weight ratio are 90:5:
5；It is lithium metal to electrode；Electrolyte is 1mol/L LiPF6EC/DMC (volume ratios 1:1) solution；Barrier film is Cellgard
2400 micro-pore septums.The current density of battery testing is 0.1C and 1C, and discharge voltage range is 3~1.5V.
Comparative example 2
Fluorocarbons is uniformly mixed with glucose by the proportioning that Glucose Carbon weight content is 5%, then at 450 DEG C of heat
5h is managed, the fluorocarbons positive electrode of Glucose Carbon cladding is obtained after sieving.
According to the battery condition of embodiment 1, the fluorocarbons positive electrode of the Glucose Carbon of test comparison example 2 cladding is in 2032 types
Discharge performance in button cell.
As depicted in figs. 1 and 2,2032 type batteries of each embodiment and comparative example assembling are carried out into 0.1C and 1C respectively to discharge
Test and comparison, the discharge voltage plateau and capacity data of material are listed in the following table.
As can be seen from the table, the 0.1C discharge voltage plateaus of fluorinated carbon material are 2.45V in comparative example 1, and specific capacity is
794.3mAh/g, and CFx-C material discharging voltage platforms obtained by embodiment are between 2.60~2.69V, improve 0.15~
0.24V, the almost free of losses of its specific capacity, or even material 830.3mAh/g prepared by embodiment 1 specific capacity very close fluorine
Change the theoretical specific capacity (860mAh/g) of carbon material.In addition, fluorinated carbon material putting in the larger discharge currents of 1C in comparative example 1
Piezoelectric voltage platform is 1.89V, specific capacity 468.2mAh/g, and CFx-C material discharging voltage platforms obtained by embodiment are more than
Between 2.3V, improve that 0.4V is more, and its specific capacity is more than 693mAh/g, improves nearly 200~300mAh/g.However, comparative example 2
Using glucose as carbon source, the specific capacity and discharge voltage plateau of the fluorinated carbon material of gained carbon coating have been lifted, but are carried
Increasing degree degree is less than the fluorocarbons of pitch carbon coating, and the gap in larger discharge current becomes apparent.As a result show, this hair
After the bright pitch carbon coating fluorocarbons, the discharge voltage plateau of material can be greatly improved, keep the high low discharging current of material
Specific capacity and significantly improve larger current specific discharge capacity.
Claims (7)
1. a kind of preparation method of pitch carbon coating fluorocarbons positive electrode, it is characterised in that comprise the following steps：
1) fluorocarbons is well mixed with pitch, obtains material I；
2) the material I is heat-treated under atmosphere of inert gases protection, then through cooling down, sieving to obtain the pitch-coating fluorination
Carbon positive electrode.
2. preparation method as claimed in claim 1, it is characterised in that：Carbonaceous amount in step 1) in pitch accounts for fluorocarbons quality
Percentage≤15%；
Carbonaceous amount in pitch refers to：Pitch is handled into 1h under 500 DEG C, nitrogen atmosphere, obtains the quality of product.
3. preparation method as claimed in claim 1, it is characterised in that：The condition of step 2) heat treatment is in 300~550 DEG C of conditions
0.5~10h of lower processing.
4. preparation method as claimed in claim 1, it is characterised in that：The inert gas is argon gas or nitrogen.
5. preparation method as claimed in claim 1, it is characterised in that：The fluorocarbons is fluorographite, fluorination coke, fluorination charcoal
Any one in black, carbon fluoride nano-tube and fluorinated graphene or any several mixtures with any ratio.
6. preparation method as claimed in claim 1, it is characterised in that：The pitch is asphalt, coal tar pitch and bitumen
Any one or any several mixtures with any ratio.
A kind of 7. pitch carbon coating fluorocarbons positive electrode, it is characterised in that：The quality of the surface coated bitumencarb of fluorocarbons accounts for
Mass percent≤15% of fluorocarbons.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710621698.2A CN107482187B (en) | 2017-07-27 | 2017-07-27 | Asphalt carbon-coated carbon fluoride anode material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710621698.2A CN107482187B (en) | 2017-07-27 | 2017-07-27 | Asphalt carbon-coated carbon fluoride anode material and preparation method thereof |
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| Publication Number | Publication Date |
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| CN107482187A true CN107482187A (en) | 2017-12-15 |
| CN107482187B CN107482187B (en) | 2020-07-03 |
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| CN201710621698.2A Active CN107482187B (en) | 2017-07-27 | 2017-07-27 | Asphalt carbon-coated carbon fluoride anode material and preparation method thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109461923A (en) * | 2018-11-13 | 2019-03-12 | 山东重山光电材料股份有限公司 | A kind of lithium primary battery compound fluorocarbons positive electrode and its preparation method and application |
| CN110380014A (en) * | 2019-04-26 | 2019-10-25 | 中国航发北京航空材料研究院 | A kind of preparation method of the composite anode material for lithium sulfur battery of high stability |
| CN111628168A (en) * | 2020-06-20 | 2020-09-04 | 沈晨 | Novel graphite fluoride composite lithium ion battery cathode material and preparation method thereof |
| CN112038650A (en) * | 2020-07-28 | 2020-12-04 | 天津力神电池股份有限公司 | Flexible package lithium fluorocarbon primary battery |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105161681A (en) * | 2015-08-10 | 2015-12-16 | 湘潭大学 | Microencapsulated carbon-coated carbon fluoride cathode material and preparation method thereof |
| CN106252596A (en) * | 2016-08-05 | 2016-12-21 | 深圳市贝特瑞新能源材料股份有限公司 | Soft carbon graphite composite negative pole material, preparation method and lithium ion battery |
-
2017
- 2017-07-27 CN CN201710621698.2A patent/CN107482187B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105161681A (en) * | 2015-08-10 | 2015-12-16 | 湘潭大学 | Microencapsulated carbon-coated carbon fluoride cathode material and preparation method thereof |
| CN106252596A (en) * | 2016-08-05 | 2016-12-21 | 深圳市贝特瑞新能源材料股份有限公司 | Soft carbon graphite composite negative pole material, preparation method and lithium ion battery |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109461923A (en) * | 2018-11-13 | 2019-03-12 | 山东重山光电材料股份有限公司 | A kind of lithium primary battery compound fluorocarbons positive electrode and its preparation method and application |
| CN110380014A (en) * | 2019-04-26 | 2019-10-25 | 中国航发北京航空材料研究院 | A kind of preparation method of the composite anode material for lithium sulfur battery of high stability |
| CN111628168A (en) * | 2020-06-20 | 2020-09-04 | 沈晨 | Novel graphite fluoride composite lithium ion battery cathode material and preparation method thereof |
| CN112038650A (en) * | 2020-07-28 | 2020-12-04 | 天津力神电池股份有限公司 | Flexible package lithium fluorocarbon primary battery |
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| CN107482187B (en) | 2020-07-03 |
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Address after: No.8 Haitai Avenue, Huayuan Industrial Park, Binhai New Area, Tianjin, 300384 Patentee after: Tianjin Bamo Technology Co.,Ltd. Address before: No.8 Haitai Avenue, Huayuan Industrial Park, Binhai New Area, Tianjin, 300384 Patentee before: TIANJIN B & M SCIENCE AND TECHNOLOGY JOINT-STOCK Co.,Ltd. |
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Address after: No.8 Haitai Avenue, Huayuan Industrial Park, Binhai New Area, Tianjin, 300384 Patentee after: Tianjin Bamo Technology Co.,Ltd. Address before: No.8 Haitai Avenue, Huayuan Industrial Park, Binhai New Area, Tianjin, 300384 Patentee before: TIANJIN B & M SCIENCE AND TECHNOLOGY JOINT-STOCK Co.,Ltd. |