CN109167040A - Method for applying carbon fluoride additive to lithium-sulfur battery and application of carbon fluoride additive - Google Patents
Method for applying carbon fluoride additive to lithium-sulfur battery and application of carbon fluoride additive Download PDFInfo
- Publication number
- CN109167040A CN109167040A CN201810986904.4A CN201810986904A CN109167040A CN 109167040 A CN109167040 A CN 109167040A CN 201810986904 A CN201810986904 A CN 201810986904A CN 109167040 A CN109167040 A CN 109167040A
- Authority
- CN
- China
- Prior art keywords
- lithium
- sulfur cell
- fluorination
- carbon
- fluorocarbons
- 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.)
- Pending
Links
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 239000000654 additive Substances 0.000 title claims abstract description 28
- 230000000996 additive effect Effects 0.000 title claims abstract description 28
- 238000000034 method Methods 0.000 title claims abstract description 18
- TXEYQDLBPFQVAA-UHFFFAOYSA-N tetrafluoromethane Chemical compound FC(F)(F)F TXEYQDLBPFQVAA-UHFFFAOYSA-N 0.000 title abstract 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 17
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000002033 PVDF binder Substances 0.000 claims abstract description 7
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims abstract description 7
- 239000011230 binding agent Substances 0.000 claims abstract description 4
- 238000003682 fluorination reaction Methods 0.000 claims description 20
- 239000005864 Sulphur Substances 0.000 claims description 10
- GLNWILHOFOBOFD-UHFFFAOYSA-N lithium sulfide Chemical class [Li+].[Li+].[S-2] GLNWILHOFOBOFD-UHFFFAOYSA-N 0.000 claims description 10
- 239000011149 active material Substances 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- 238000007599 discharging Methods 0.000 claims description 4
- 230000000694 effects Effects 0.000 claims description 4
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 238000004891 communication Methods 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 239000000571 coke Substances 0.000 claims description 2
- 230000005611 electricity Effects 0.000 claims description 2
- 229910002804 graphite Inorganic materials 0.000 claims description 2
- 239000010439 graphite Substances 0.000 claims description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 2
- 239000013081 microcrystal Substances 0.000 claims description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims 1
- 239000006229 carbon black Substances 0.000 claims 1
- 229910052731 fluorine Inorganic materials 0.000 claims 1
- 239000011737 fluorine Substances 0.000 claims 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 8
- 229910052744 lithium Inorganic materials 0.000 abstract description 8
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 238000004146 energy storage Methods 0.000 abstract description 5
- 238000006243 chemical reaction Methods 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 3
- 239000010405 anode material Substances 0.000 abstract description 2
- 239000013543 active substance Substances 0.000 abstract 1
- 230000002349 favourable effect Effects 0.000 abstract 1
- 239000005077 polysulfide Substances 0.000 abstract 1
- 229920001021 polysulfide Polymers 0.000 abstract 1
- 150000008117 polysulfides Polymers 0.000 abstract 1
- 229910052717 sulfur Inorganic materials 0.000 abstract 1
- 239000011593 sulfur Substances 0.000 abstract 1
- 239000006258 conductive agent Substances 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 5
- 239000005030 aluminium foil Substances 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 description 4
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Inorganic materials [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 4
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000000047 product Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 150000004040 pyrrolidinones Chemical class 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- OXHNLMTVIGZXSG-UHFFFAOYSA-N 1-Methylpyrrole Chemical compound CN1C=CC=C1 OXHNLMTVIGZXSG-UHFFFAOYSA-N 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000007806 chemical reaction intermediate Substances 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000005184 irreversible process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M6/00—Primary cells; Manufacture thereof
- H01M6/52—Reclaiming serviceable parts of waste cells or batteries, e.g. recycling
-
- 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
- H01M4/362—Composites
- H01M4/364—Composites as mixtures
-
- 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
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
-
- 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
- H01M4/581—Chalcogenides or intercalation compounds thereof
- H01M4/5815—Sulfides
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- 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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/84—Recycling of batteries or fuel cells
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Composite Materials (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Sustainable Development (AREA)
- Inorganic Chemistry (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to an additive which can be used as a lithium-sulfur battery anode material and performance comparison thereof under different proportions, belonging to the field of energy storage. The carbon fluoride, active substance sulfur, conductive carbon and binder PVDF are mechanically ground to be compounded to manufacture the lithium-sulfur battery, and the cycle life and the rate capability of the lithium-sulfur battery are improved by using fluorine-doped carbon generated by carbon fluoride discharge. The carbon fluoride as an additive of the lithium-sulfur battery can not only provide additional conductive carbon at the positive electrode, but also absorb lithium polysulfide by the fluorine-doped carbon. The lithium-sulfur battery prepared by using the additive has the advantages of higher capacity, longer cycle life, stable charge and discharge efficiency, easy obtainment and low cost of raw materials, simple production process and harmless reaction process, and the advantages are favorable for the application of the method to industrial actual production.
Description
Technical field
The present invention relates to the performances under additive and its different ratio that one kind can be used as lithium sulfur battery anode material to compare,
Belong to energy storage field.
Background technique
In the past few decades, the safety of lithium ion battery Yin Qigao, and be widely used in 3C Product (computer,
Communication and consumption electronic product).But the energy density of commercial li-ion battery is lower at present, onlyNothing
Method meets the demand of growing emerging large-scale energy storage technology, such as electric car and power grid energy storage etc..In numerous elder generations
Into rechargeable battery system in, lithium sulphur (Li-S) battery is by extensive concern and is studied, because it is with high theoretical specific volume
AmountHigh theoretical specific energy (2500W h-1) and sulphur is very rich on earth, cheap, nontoxic, ring
Border is friendly.
Although lithium-sulfur cell has the advantages that so many, there is also many problems to restrict its commercialization.These are asked
Topic is as described below: 1) active material sulphur and electric discharge final product lithium sulfide are nonconducting, it is low which results in the utilization rate of sulphur and
Special capacity fade is very fast；2) reaction of Salmon-Saxl, which generates lithium sulfide, leads to serious volume expansion, and general 80%；3) reaction intermediate is long
The more lithium sulfides of chain are soluble in electrolyte, lead to " shuttle effect "；4) problems of cathode of lithium itself are badly in need of solving, such as lithium branch
Brilliant growth.These problems lead to low coulombic efficiency, capacity quickly and reduce low with active material utilization efficiency.Therefore it improves and leads
It is electrically protected with cathode of lithium, raw material sources are extensive, and the simple lithium-sulfur cell of production technology is particularly important.
Summary of the invention
The purpose of the present invention is using fluorocarbons as additive, the method for the commercially viable lithium-sulfur cell of exploitation high-performance, and
And a kind of method of electrode material waste waste utilization is provided, i.e., after Li/ fluorocarbons one-shot battery is finished, generate anode waste
Play the role of promoting chemical property in lithium-sulfur cell again.
To solve technical problem of the invention, the technical scheme is that fluorination carbonaceous additive is for lithium-sulfur cell
Fluorocarbons is added to active material sulphur, conductive carbon and binder PVDF and matched in the mixture for 7:2:1 by method, carries out machine
Tool ground and mixed makes lithium-sulfur cell as positive electrode after mixing, is promoted using the Fluorin doped carbon that fluorocarbons electric discharge generates
The cycle life and high rate performance of lithium-sulfur cell.
Preferably, the fluorocarbons includes fluorographite, fluorination coke, fluorinated carbon fiber, fluorination carbosphere, fluorination charcoal
Black, fluorination micro crystal graphite or fluorographite microplate.
Preferably, 5-20% fluorination carbonaceous additive is added in lithium-sulfur cell.
Preferably, 10% fluorination carbonaceous additive is added in lithium-sulfur cell.
Preferably, the fluorocarbons reaction generates carbon, increases the electric conductivity of galvanic electricity pole.
Preferably, the Fluorin doped carbon of the generation can adsorb more lithium sulfides, thus inhibit the shuttle effect of more lithium sulfides,
Improve the chemical property of lithium-sulfur cell.
Preferably, the charging/discharging voltage of the lithium-sulfur cell is 1.8-3.0V.
Preferably, it can be used as energy storage to apply in computer, communication and consumer electronics sector.
A kind of preparation method of high-performance lithium-sulfur cell, preparation process are as follows: fluorocarbons (expedition group) is used as lithium sulphur
The anode additive of battery, elemental sulfur are used as the positive active material of lithium-sulfur cell.
The method for preparing lithium-sulfur cell, first, in accordance with active material: conductive agent: binder mass ratio is that 7:2:1 will be positive
After material sulphur, conductive agent Super P and polyvinylidene fluoride mechanical lapping, then into the mixture after grinding it is added 0/5/10/
20% fluorocarbons is uniformly mixed in solvent N-methyl pyrilidone, is uniformly mixed to obtain and is dispersed uniform slurry, then will
Uniformly it is coated on utter misery aluminium foil.Then the electrode slice made is dried into 12h in 60 DEG C of normal drying casees, be then transferred to
12h is dried in 60 DEG C of vacuum drying oven.Using metal lithium sheet as cathode, 1.0M LiTFSI, 5%LiNO3DME:DOL=1:
1Vol% is electrolyte, and diaphragm uses commercialized 2400 diaphragm of Celgar, and battery case model 2025, in glove box, (oxygen contains
Amount is less than 0.5ppm, and water content is less than assembling button cell in 0.5ppm).
Battery assembly carries out rate charge-discharge on cell tester (the blue electric battery test system in Wuhan) after completing and follows
Ring test, operating voltage 1.8-3V, data acquisition are drawn by origin data processing software after completing, are analyzed.
The utility model has the advantages that
Fluorocarbons can not only provide additional conductive carbon, but also Fluorin doped carbon as lithium-sulfur cell additive in anode
More lithium sulfides can also be adsorbed.The lithium-sulfur cell capacity with higher prepared using the additive, cycle life is longer, stablizes
Efficiency for charge-discharge, furthermore raw material be easy to get and low cost, the simplicity of production technology, reaction process is innoxious, these advantages
Be conducive to this method and be applied to industrialization actual production.
Fluorocarbons has been used as being commercialized disposable lithium-battery, can generate LiF and C (Fluorin doped carbon) when discharging, so not
It only causes to waste and pollute, and also increase its cost in this way.Based on this, we want to be promoted using the discharging product of fluorocarbons
The chemical property of lithium-sulfur cell, cardinal principle are that fluorocarbons is made into slurry with sulphur mixing as additive, by it, are then done
At electrode slice, in first discharge process of lithium-sulfur cell, fluorocarbons generates LiF and C, and this is an irreversible process,
This is also equivalent to increase conductive carbon in anode, and Fluorin doped carbon can adsorb more lithium sulfides, inhibit the shuttle of more lithium sulfides
Effect.The chemical property of lithium-sulfur cell not only can be greatly improved, and the cost of lithium-sulfur cell can be reduced.
Detailed description of the invention
Fig. 1 is fluorocarbons X-ray diffractogram.
Fig. 2 is fluorocarbons as additive and additive-free lithium-sulfur cell long circulating performance map.
Fig. 3 is fluorocarbons as additive and additive-free lithium-sulfur cell high rate performance figure.
Fig. 4 is fluorocarbons as the impedance after additive and additive-free lithium-sulfur cell circulation.
Specific embodiment
Below in conjunction with specific implementation example, it is intended to further illustrate that the present invention is not intended to limit the present invention.
Embodiment 1
5mg fluorocarbons is weighed, 70mg sulphur, 20mg conductive agent Super P, 10mg polyvinylidene fluoride is in Solvents N-methyl pyrrole
It is uniformly mixed, will uniformly be coated on utter misery aluminium foil, then by the electrode slice made in 60 DEG C of normal dryings in pyrrolidone
12h is dried in case, is then transferred in 60 DEG C of vacuum drying oven and is dried 12h.Using metal lithium sheet as cathode, 1.0M LiTFSI, 5%
LiNO3DME:DOL=1:1Vol% is electrolyte, and diaphragm uses commercialized 2400 diaphragm of Celgar, battery case model
2025, button cell is assembled in glove box (oxygen content is less than 0.5ppm, and water content is less than 0.5ppm).
Battery assembly carries out rate charge-discharge on cell tester (the blue electric battery test system in Wuhan) after completing and follows
Ring test, operating voltage 1.8-3V, data acquisition are drawn by origin data processing software after completing, are analyzed.
When battery uses 0.1C charge and discharge in blue electric system, first circle specific discharge capacity reaches 719.8mAh g-1, then use
When 0.5C charge and discharge, third circle specific discharge capacity 508.4mAh g-1, after 150 circles, specific discharge capacity also reaches 464.2mAh
g-1；When with 1C charge and discharge, first circle specific capacity is 439.3mAh g-1, after 400 enclose, the also surplus 248.5mAh g of specific capacity-1；Multiplying power
Impedance afterwards is 6 Ω.
Embodiment 2
10mg fluorocarbons is weighed, 70mg sulphur, 20mg conductive agent Super P, 10mg polyvinylidene fluoride is in Solvents N-methyl
It is uniformly mixed, will uniformly be coated on utter misery aluminium foil in pyrrolidones, it is then that the electrode slice made is common dry at 60 DEG C
12h is dried in dry case, is then transferred in 60 DEG C of vacuum drying oven and dries 12h.Using metal lithium sheet as cathode, 1.0M LiTFSI,
5%LiNO3DME:DOL=1:1Vol% is electrolyte, and diaphragm uses commercialized 2400 diaphragm of Celgar, battery case model
It is 2025, assembles button cell in glove box (oxygen content is less than 0.5ppm, and water content is less than 0.5ppm).
Battery assembly carries out rate charge-discharge on cell tester (the blue electric battery test system in Wuhan) after completing and follows
Ring test, operating voltage 1.8-3V, data acquisition are drawn by origin data processing software after completing, are analyzed.
For battery when using 0.1C charge and discharge in blue electric system, first circle specific discharge capacity reaches 901.3mAh g-1, then use 0.5C
When charge and discharge, third circle specific discharge capacity 577.3mAh g-1, after 150 circles, specific discharge capacity also reaches 508.3mAh g-1；
When with 1C charge and discharge, first circle specific capacity is 486.9mAh g-1, after 400 enclose, the also surplus 338.4mAh g of specific capacity-1。
Embodiment 3
20mg fluorocarbons is weighed, 70mg sulphur, 20mg conductive agent Super P, 10mg polyvinylidene fluoride is in Solvents N-methyl
It is uniformly mixed, will uniformly be coated on utter misery aluminium foil in pyrrolidones, it is then that the electrode slice made is common dry at 60 DEG C
12h is dried in dry case, is then transferred in 60 DEG C of vacuum drying oven and dries 12h.Using metal lithium sheet as cathode, 1.0M LiTFSI,
5%LiNO3DME:DOL=1:1Vol% is electrolyte, and diaphragm uses commercialized 2400 diaphragm of Celgar, battery case model
It is 2025, assembles button cell in glove box (oxygen content is less than 0.5ppm, and water content is less than 0.5ppm).
Battery assembly carries out rate charge-discharge on cell tester (the blue electric battery test system in Wuhan) after completing and follows
Ring test, operating voltage 1.8-3V, data acquisition are drawn by origin data processing software after completing, are analyzed.
For battery when using 0.1C charge and discharge in blue electric system, first circle specific discharge capacity reaches 862.5mAh g-1, then use 0.5C
When charge and discharge, third circle specific discharge capacity 616.2mAh g-1, after 150 circles, specific discharge capacity also reaches 488.1mAh g-1；
When with 1C charge and discharge, first circle specific capacity is 555.4mAh g-1, after 400 enclose, the also surplus 346.9mAh g of specific capacity-1；After multiplying power
Impedance is 2 Ω.
Of the invention is not limited to the above embodiment the specific technical solution, all technologies formed using equivalent replacement
Scheme be the present invention claims protection scope.
Claims (8)
1. it is a kind of fluorination carbonaceous additive be used for lithium-sulfur cell method, it is characterised in that: by fluorocarbons be added to active material sulphur,
Conductive carbon and binder PVDF proportion are to carry out mechanical lapping mixing in the mixture of 7:2:1, and positive electrode system is used as after mixing
Make lithium-sulfur cell, the cycle life and high rate performance of lithium-sulfur cell are promoted using the Fluorin doped carbon that fluorocarbons electric discharge generates.
2. fluorination carbonaceous additive according to claim 1 is used for lithium-sulfur cell method, it is characterised in that: the fluorocarbons packet
It is micro- to include fluorographite, fluorination coke, fluorinated carbon fiber, fluorination carbosphere, fluorination carbon black, fluorination micro crystal graphite or fluorographite
Piece.
3. fluorination carbonaceous additive according to claim 1 is used for lithium-sulfur cell method, it is characterised in that: 5-20% to be fluorinated
Carbonaceous additive is added in lithium-sulfur cell.
4. fluorination carbonaceous additive according to claim 3 is used for lithium-sulfur cell method, it is characterised in that: by 10% fluorocarbons
Additive is added in lithium-sulfur cell.
5. fluorination carbonaceous additive according to claim 1 is used for lithium-sulfur cell method, it is characterised in that: the fluorocarbons is anti-
Carbon should be generated, the electric conductivity of galvanic electricity pole is increased.
6. fluorination carbonaceous additive according to claim 1 is used for lithium-sulfur cell method, it is characterised in that: the fluorine of the generation
Doped carbon can adsorb more lithium sulfides, to inhibit the shuttle effect of more lithium sulfides, improve the chemical property of lithium-sulfur cell.
7. fluorination carbonaceous additive according to claim 1 is used for lithium-sulfur cell method, it is characterised in that: the lithium-sulfur cell
Charging/discharging voltage be 1.8-3.0V.
8. prepared fluorination carbonaceous additive is used for the application of lithium-sulfur cell according to claim 1, it is characterised in that: can be used as energy
Source storage is applied in computer, communication and consumer electronics sector.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810986904.4A CN109167040A (en) | 2018-08-28 | 2018-08-28 | Method for applying carbon fluoride additive to lithium-sulfur battery and application of carbon fluoride additive |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810986904.4A CN109167040A (en) | 2018-08-28 | 2018-08-28 | Method for applying carbon fluoride additive to lithium-sulfur battery and application of carbon fluoride additive |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109167040A true CN109167040A (en) | 2019-01-08 |
Family
ID=64897001
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810986904.4A Pending CN109167040A (en) | 2018-08-28 | 2018-08-28 | Method for applying carbon fluoride additive to lithium-sulfur battery and application of carbon fluoride additive |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109167040A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109921004A (en) * | 2019-03-19 | 2019-06-21 | 北京化工大学 | A kind of lithium sulfur battery anode material and its application |
| CN111628166A (en) * | 2020-06-04 | 2020-09-04 | 合肥工业大学 | Three-dimensional lithium sulfide electrode for lithium-sulfur battery and preparation method thereof |
| CN111628150A (en) * | 2020-06-04 | 2020-09-04 | 合肥工业大学 | Carbon-coated lithium sulfide composite electrode for lithium-sulfur battery and preparation method thereof |
| CN114784452A (en) * | 2022-05-24 | 2022-07-22 | 南京工业大学 | Method for preparing lithium-sulfur battery diaphragm material by using fluorine-containing covalent organic framework material |
| CN114824587A (en) * | 2022-05-30 | 2022-07-29 | 中国科学院长春应用化学研究所 | Lithium air/carbon fluoride composite battery |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104716296A (en) * | 2013-12-11 | 2015-06-17 | 上海空间电源研究所 | Sulfur-containing composite anode, preparation method thereof and lithium-sulfur battery using sulfur-containing composite anode as anode |
| CN106169561A (en) * | 2016-09-30 | 2016-11-30 | 上海空间电源研究所 | A kind of sulfur system anode composite pole piece, the battery comprising it and preparation method thereof |
| CN107316967A (en) * | 2017-06-26 | 2017-11-03 | 上海空间电源研究所 | A kind of barrier film, preparation method and the usage for including active interlayer |
| CN107895794A (en) * | 2017-11-23 | 2018-04-10 | 中国航发北京航空材料研究院 | A kind of high specific energy lithium fluorocarbon battery |
| CN107910502A (en) * | 2017-11-15 | 2018-04-13 | 上海空间电源研究所 | A kind of lithium battery anode composite manufacture method and the battery |
-
2018
- 2018-08-28 CN CN201810986904.4A patent/CN109167040A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104716296A (en) * | 2013-12-11 | 2015-06-17 | 上海空间电源研究所 | Sulfur-containing composite anode, preparation method thereof and lithium-sulfur battery using sulfur-containing composite anode as anode |
| CN106169561A (en) * | 2016-09-30 | 2016-11-30 | 上海空间电源研究所 | A kind of sulfur system anode composite pole piece, the battery comprising it and preparation method thereof |
| CN107316967A (en) * | 2017-06-26 | 2017-11-03 | 上海空间电源研究所 | A kind of barrier film, preparation method and the usage for including active interlayer |
| CN107910502A (en) * | 2017-11-15 | 2018-04-13 | 上海空间电源研究所 | A kind of lithium battery anode composite manufacture method and the battery |
| CN107895794A (en) * | 2017-11-23 | 2018-04-10 | 中国航发北京航空材料研究院 | A kind of high specific energy lithium fluorocarbon battery |
Non-Patent Citations (4)
| Title |
|---|
| 吴锋 等: "化学结合力载体在锂硫电池中的应用", 《化学进展》 * |
| 李国欣 主编: "《新型化学电源技术概论》", 31 May 2007, 上海科学技术出版社 * |
| 裴海娟 等: "导电碳修饰隔膜在高硫载量锂硫电池中的作用", 《储能科学与技术》 * |
| 陈子冲 等: "锂硫电池硫正极材料研究进展", 《材料导报A：综述篇》 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109921004A (en) * | 2019-03-19 | 2019-06-21 | 北京化工大学 | A kind of lithium sulfur battery anode material and its application |
| CN109921004B (en) * | 2019-03-19 | 2021-01-12 | 北京化工大学 | Lithium-sulfur battery positive electrode material and application thereof |
| CN111628166A (en) * | 2020-06-04 | 2020-09-04 | 合肥工业大学 | Three-dimensional lithium sulfide electrode for lithium-sulfur battery and preparation method thereof |
| CN111628150A (en) * | 2020-06-04 | 2020-09-04 | 合肥工业大学 | Carbon-coated lithium sulfide composite electrode for lithium-sulfur battery and preparation method thereof |
| CN111628150B (en) * | 2020-06-04 | 2021-10-08 | 合肥工业大学 | Carbon-coated lithium sulfide composite electrode for lithium-sulfur battery and preparation method thereof |
| CN114784452A (en) * | 2022-05-24 | 2022-07-22 | 南京工业大学 | Method for preparing lithium-sulfur battery diaphragm material by using fluorine-containing covalent organic framework material |
| CN114784452B (en) * | 2022-05-24 | 2023-09-26 | 南京工业大学 | Method for preparing lithium-sulfur battery diaphragm material by using fluorine-containing covalent organic framework material |
| CN114824587A (en) * | 2022-05-30 | 2022-07-29 | 中国科学院长春应用化学研究所 | Lithium air/carbon fluoride composite battery |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103700820B (en) | A kind of lithium ion selenium battery with long service life | |
| CN110416531B (en) | Bismuth oxyhalide aqueous zinc ion secondary battery positive electrode and preparation method and application thereof | |
| CN103435105B (en) | A kind of ferriferous oxide/carbon composition lithium ion battery cathode material and its preparation method and application | |
| CN105489901B (en) | A kind of preparation method and applications of lithium-sulfur cell three-dimensional carbon collector | |
| CN109004199B (en) | Preparation method of biomass hard carbon material for negative electrode of sodium-ion battery | |
| CN109167040A (en) | Method for applying carbon fluoride additive to lithium-sulfur battery and application of carbon fluoride additive | |
| CN110148787B (en) | Electrolyte for improving capacity of lithium-sulfur battery and lithium-sulfur battery | |
| CN102082259A (en) | Lithium secondary battery electrodes and production method thereof | |
| CN102244288B (en) | Lithium-phosphorus secondary battery | |
| CN110611084B (en) | Lithium-sulfur secondary battery with long cycle life and 100% coulombic efficiency | |
| CN107946538A (en) | Lithiumation sulfur electrode and preparation method and application | |
| CN108922788A (en) | A kind of PEDOT@Na3(VOPO4)2F composite material, preparation method and its application | |
| CN104617283A (en) | Lithium-sulfur battery carbon fiber reinforced three-dimensional graphene-sulfur positive electrode material, preparation method of material and preparation method of positive electrode | |
| CN109704302A (en) | A kind of phosphorus doping porous carbon materials and its preparation and the application in lithium-sulfur cell coated separator | |
| CN103427068B (en) | A kind of positive electrode and preparation method thereof for lithium-sulfur cell | |
| CN107946564B (en) | Rich in Na4Mn2O5/Na0.7MnO2Composite material and preparation method and application thereof | |
| CN109286002B (en) | Multi-bark biomass carbon-loaded red phosphorus sodium ion battery negative electrode material and preparation method thereof | |
| CN102024989A (en) | Preparation method of high-voltage lithium-ion battery | |
| CN104183836B (en) | A kind of lithium-sulfur cell anode composite material | |
| CN109962231A (en) | Metal foil is used as lanthanum ion secondary battery negative pole and lanthanum ion secondary cell and preparation method thereof | |
| CN105680016B (en) | One kind contains addition of C o3O4Lithium sulfur battery anode material and preparation method | |
| CN108987755A (en) | Method for applying lignosulfonate as binder to lithium-sulfur battery and application of lignosulfonate | |
| CN114284476A (en) | Preparation method of carbon composite sodium-ion battery positive electrode material | |
| CN103367728A (en) | Activated natural graphite modified Li2FeSiO4 cathode material and its preparation method | |
| CN108258244B (en) | Novel lithium ion/potassium ion battery negative electrode material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20190108 |
|
| RJ01 | Rejection of invention patent application after publication |