CN106711430A - Production method of lithium/carbon fiber or porous carbon paper/copper foil composite negative electrode used for lithium-sulfur battery - Google Patents
Production method of lithium/carbon fiber or porous carbon paper/copper foil composite negative electrode used for lithium-sulfur battery Download PDFInfo
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- 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
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- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a production method of a lithium/carbon fiber or porous carbon paper/copper foil composite negative electrode used for a lithium-sulfur battery. The method comprises the following steps: producing a carbon fiber/copper foil negative electrode from carbon fibers, conductive carbon and a binder through a coating technology, and embedding and depositing lithium through an electrochemical technology to produce the lithium/carbon fiber/copper foil composite negative electrode; or superposing copper foil and porous carbon paper to produce a porous carbon paper/copper foil negative electrode, and embedding and depositing lithium through the electrochemical technology to produce the lithium/porous carbon paper/copper foil composite negative electrode. The lithium/carbon fiber or porous carbon paper/copper foil composite negative electrode is flexible, can be easily reeled, can be used in the lithium-sulfur battery, and has the advantages of dendrite growth inhibition, high coulombic efficiency, high specific capacity and good electrochemical characteristics.
Description
Technical field
The present invention relates to a kind of preparation method of lithium-sulfur cell negative pole, and in particular to suppress lithium dendrite growth, coulomb high effect
The preparation method of rate, the lithium/carbon fiber of height ratio capacity or porous carbon paper/Copper Foil composite negative pole, can be applied to lithium sulphur as negative pole
In battery, belong to lithium metal battery technical field.
Background technology
The successful commercialization of lithium ion battery, make portable type electronic product and electronic carriage of vehicle have it is quick development and
Significant progress.But with the development of science and technology, different industries propose requirement higher, traditional graphite cathode to battery performance
(372mAh/g) has been difficult to meet demand of the high specific energy batteries of new generation to negative material.Lithium an- ode has high power capacity
(3860mAh/g), low potential (- 3.040V vs standard hydrogen electrodes) and low density (0.53g cm-2) become ratio high of future generation
One critically important negative material of energy battery development.With lithium metal as negative pole, the lithium ion having been commercialized not only is can apply to
Battery, and have become high specific energy batteries of future generation such as lithium-sulfur cell (2600wh/kg), lithium sky battery (5210wh/kg) etc.
The important selection of negative material.
Lithium an- ode possesses so excellent chemical property, and commercialization is but failed always, is primarily due to exist
Hinder the obstacle of its practical application.Wherein major obstacle is that negative terminal surface lithium nonuniform deposition forms Li dendrite, lithium branch when charging
Crystalline substance may puncture barrier film causes battery short circuit, produces the potential dangers such as combustion explosion；During electric discharge, Li dendrite fusing departs from negative pole and subtracts
The effective rate of utilization of active material lithium when having lacked recyclable discharge and recharge, reduces the coulombic efficiency and capacity of negative pole.
In order to solve lithium an- ode problems faced, researcher has attempted many schemes：
1) electrolyte is modified.Such as electrolysis additive, such method is intended to adjust lithium metal surface membrane component, or regulates and controls
Lithium surface field and distribution of charges in electrolyte, and reach and alleviate the effect that Li dendrite is produced.Lithium deposition under the method,
To the remission effect that has of Li dendrite under low current density and in the short time, but at higher current densities and for a long time
But effective suppression Li dendrite is difficult under lithium deposition, such as most of additives are constantly consumed during circulating battery, influence
The electrochemical stability of long-time lithium deposition.
2) using solid electrolyte or gel electrolyte etc..Such electrolyte possesses certain intensity, can effectively hinder
Gear Li dendrite is punctured to barrier film, but because lithium ion spreads more difficult in such electrolyte, causes the power density of battery
It is greatly lowered.Additionally, such electrolyte preparation technology is cumbersome, it is expensive.
3) lithium piece surface coating modification.Coating modification such as is carried out to lithium surface with polymer, the physics using clad is strong
Degree or chemical characteristic alleviate the generation of Li dendrite.But clad, because of its insulating properties and limited strength, such method exists
The effective generation for suppressing Li dendrite is still difficult under high current density and under prolonged lithium deposition.
4) lithium composite negative pole is used.The research of lithium composite negative pole is increasingly becoming focus in recent years.There is research small in recent years
Group is attempted being prepared containing cathode of lithium with three-dimensional porous fiber composite after lithium metal is fused into liquid, and this negative pole can effectively suppress lithium
The generation of dendrite, reduces the polarization potential of battery, while can be bent in 0 ° -180 °, but the electrochemistry during bending
Performance loss rate is up to 50%.Additionally, composite negative pole uses lithium metal smelting process, the harshnesses such as inert atmosphere are not only needed
Condition, and most of fibers are too poor with liquid lithium compatibility, it is difficult to prepare homogeneous composite negative pole, simultaneously as compound
The presence of bulk lithium metal in negative pole, the flexibility of electrode also reaches far away the requirement of industrial winding.There is research group's utilizationization
In the micron order fiber copper of copper foil surface deposited porous, this deposition substrate improves the stable circulation of lithium an- ode to method
Property, in the half-cell constituted with lithium piece, coulombic efficiency can reach 97%, but due to the high density property of copper, this deposition substrate
Micron copper fiber will certainly increase considerably the quality of deposition substrate, while this deposition substrate preparation technology is cumbersome, price is held high
It is expensive.
Therefore, the development that requires study has dendrite inhibition growth, coulombic efficiency high, the lithium metal composite negative pole of height ratio capacity
And its industrialized preparation method.
The content of the invention
For the problem that prior art is present, the purpose of the present invention be provide one kind possess it is flexible, can easily wind,
And lithium/carbon fiber or the preparation side of porous carbon paper/Copper Foil composite negative pole of dendrite inhibition growth, coulombic efficiency high and height ratio capacity
Method, the method is simple to operate, low cost, meets demand of industrial production.
In order to realize above-mentioned technical purpose, the invention provides a kind of lithium/carbon fiber or porous carbon for lithium-sulfur cell
The preparation method of paper/Copper Foil composite negative pole, the method is that by rubbing method prepared by carbon fiber and conductive carbon, binding agent into carbon fibre
Dimension/Copper Foil negative pole, the carbon fiber/Copper Foil negative pole is embedded in and lithium deposition by electrochemical method, obtains lithium/carbon fiber/Copper Foil
Composite negative pole；Or, Copper Foil and porous carbon quires are closed and prepares porous carbon paper/Copper Foil negative pole, the porous carbon paper/Copper Foil negative pole
It is embedded in by electrochemical method and lithium deposition, obtains lithium/porous carbon paper/Copper Foil composite negative pole.
, be coated on Copper Foil for carbon fiber and conductive carbon using binding agent by technical scheme, is obtained by drying
Carbon fiber/Copper Foil negative pole, due to conductive carbon can with carbon fiber interweave be overlapped to form one have highly porous negative pole (porosity
For 20%~99%, aperture is 1 micron~5000 microns), the embedding lithium in pole piece inside and sinker specific capacity are big, by carbon fiber/Copper Foil
Negative pole electrochemical intercalation and lithium deposition, that is, obtain lithium/carbon fiber/Copper Foil combination electrode.Lithium/carbon fiber/the Copper Foil of preparation is combined
Electrode can effectively suppress Li dendrite, show the chemical property of coulombic efficiency high, height ratio capacity.
Technical scheme, it would however also be possible to employ Copper Foil and porous carbon quires close after again by electrochemical method insertion or
Lithium deposition, makes full use of the loose structure and big specific surface area of porous carbon paper, and embedding lithium is big with sinker specific capacity, and the lithium of preparation/
Porous carbon paper/Copper Foil combination electrode, can effectively suppress Li dendrite, show the electrochemistry of coulombic efficiency high, height ratio capacity
Energy.
Preferred scheme, the mass percentage content of each active component is in the carbon fiber/Copper Foil negative pole：Binding agent
1%~20%；Carbon fiber 5%~99%；Conductive carbon 0%~90%.
More preferably scheme, the carbon fiber diameter is 0.5 μm~50 μm, length is 1 μm~5000 μm；The carbon fiber
Including biomass cracking carbon fiber (be such as carbonized cotton fiber), organic cracking carbon fiber (such as pitch, polyimides), change
Learn at least one of vapour deposition carbon fiber.
More preferably scheme, the binding agent includes Kynoar (PVDF), Sodium Polyacrylate (PAANA), polytetrafluoro
At least one of ethene (PTFE), sodium carboxymethylcellulose (CMC), sodium alginate (SA), polyvinyl alcohol (PVA).
More preferably scheme, the conductive carbon include acetylene black, conductive black, electrically conductive graphite, Ketjen black, CNT,
At least one of hard carbon.
More preferably scheme, the conductive carbon pattern is mainly particle of the diameter in 1 micron~100 micrometer ranges.
More preferably scheme, the porosity of copper foil surface material is 20%~99%, hole in the carbon fiber/Copper Foil negative pole
Footpath is 1 micron~5000 microns, thickness is 50 microns~1000 microns.
More preferably scheme, with the carbon fiber/Copper Foil negative pole as working electrode, lithium piece is to electrode, using ethers electricity
Solution liquid, is passed through constant current, the working electrode is embedded in and lithium deposition, obtains lithium/carbon fiber/Copper Foil composite negative pole；
Or, with the carbon fiber/Copper Foil negative pole as working electrode, assembled with lithium sulphur positive pole, lithium paper tinsel, barrier film and electrolyte
Into battery, the lithium paper tinsel is clipped between the working electrode and barrier film, and the battery is once discharged and charging operations, right
The working electrode is embedded in and lithium deposition, obtains lithium/carbon fiber/Copper Foil composite negative pole；
Or, with porous carbon paper/Copper Foil negative pole as working electrode, lithium piece is, to electrode, using ethers electrolyte, to be passed through perseverance
Electric current, is embedded in and lithium deposition to the working electrode, obtains lithium/porous carbon paper/Copper Foil composite negative pole；
Or, with porous carbon paper/Copper Foil negative pole as working electrode, it is assembled into lithium sulphur positive pole, lithium paper tinsel, barrier film and electrolyte
Battery, the lithium paper tinsel be clipped between the working electrode and barrier film or be clipped in the porous carbon paper of the working electrode and Copper Foil it
Between, the battery is once discharged and charging operations, the working electrode is embedded in and lithium deposition, obtain lithium/many
Hole carbon paper/Copper Foil composite negative pole.
More preferably scheme, the porous carbon paper includes foam carbon paper or porous carbon fiber paper；The hole of the porous carbon paper
Gap rate is that 20%~99%, aperture is 10 nanometers~5000 microns.
Preferred scheme, the carbon fiber/Copper Foil negative pole or porous carbon paper/Copper Foil negative pole are embedded in by electrochemical method
Include lithium salts solute, solvent and additive with the ethers electrolyte used during lithium deposition；Wherein, lithium salts solute is by double three
Fluoromethane sulfimide lithium and/or double (fluoro sulphonyl) imine lithiums are constituted, and concentration of the lithium salts solute in ethers electrolyte is 0.5
~5M；Solvent by glycol dimethyl ether and 1,3- dioxolanes by volume (0.5~2):1 composition；Additive is by lithium nitrate, nitre
At least one of sour potassium, rubidium nitrate, cesium nitrate constitute, concentration of the additive in ethers electrolyte be 0.01mol/L~
0.4mol/L。
Carbon fiber of the present invention/Copper Foil negative pole or porous carbon paper/Copper Foil negative pole are embedded in and lithium deposition in chemical method
During charging and discharging currents density be 0.1mA/cm2~4mA/cm2。
Lithium/carbon fiber of the present invention or porous carbon paper/Copper Foil composite negative pole, can be applied to lithium-sulfur cell as negative pole
In.
Compared with the prior art, the beneficial effect that technical scheme is brought：
1) lithium/carbon fiber of the invention or porous carbon paper/Copper Foil negative pole are because with high-specific surface area, high porosity and length
The specific capacity of the features such as journey is conductive, its insertion and lithium deposition is big, and the composite negative pole can effectively suppress lithium in lithium-sulfur cell
Dendrite, shows the chemical property of coulombic efficiency high, height ratio capacity.
2) lithium/carbon fiber or porous carbon paper/Copper Foil negative pole prepared by the present invention, is carried out in additive-free electrolyte
The deposition of lithium ion and dissolving, current density are 0.1mA/cm2~4mA/cm2, cathode specific capacity can reach more than 2000mAh/g,
The area specific capacity of electrode slice is in 4mAh/cm2~10mAh/cm2；The charge and discharge cycles cycle, coulombic efficiency can reach more than 50 times
To more than 95%.After appropriate additive is added in electrolyte, coulombic efficiency can reach more than 99%；Lithium/carbon fiber is more
Hole carbon paper/Copper Foil composite negative pole is assembled into lithium-sulfur cell with the pairing of sulphur carbon positive pole, after 50 circulations, with single lithium piece negative pole phase
Than the capacitance loss rate of battery can be reduced to 25% by composite negative pole from 35%.
3) lithium/carbon fiber of the invention or porous carbon paper/Copper Foil negative pole have flexibility, can arbitrarily curl, and be folded over
Chemical property loss late is low in journey, is conducive to machine-shaping, and satisfaction prepares the lithium-sulfur cell of various shapes.
4) preparation flow of lithium/carbon fiber of the invention or porous carbon paper/Copper Foil negative pole is simple, with existing lithium ion battery
Carbon anode is close, and industrialized production is carried out using existing working condition, and cost is relatively low.
Brief description of the drawings
【Fig. 1】It is the coulombic efficiency of carbonization cotton carbon fiber/Copper Foil negative pole discharge and recharge in half-cell prepared by the present invention
And charge and discharge platform.
【Fig. 2】It is the coulombic efficiency of carbon felt/Copper Foil negative pole discharge and recharge in half-cell prepared by the present invention.
【Fig. 3】It is the coulomb of polyimides carbonising carbon fibre/Copper Foil negative pole discharge and recharge in half-cell prepared by the present invention
Efficiency.
【Fig. 4】It is Comparability test blank Copper Foil and activated carbon YP50F/ Copper Foils, graphite/Copper Foil negative pole charge and discharge in half-cell
The coulombic efficiency of electricity.
Specific embodiment
Below by specific embodiment, the present invention is further illustrated, but invention protection content be not limited to it is following
Embodiment.
Embodiment 1
By thickness for the graphite cake of the cotton flat smooth of 9mm is clamped, apply certain pressure, allow cotton to keep certain
Compactness, be put into the lower 1000 DEG C of calcining 6h taking-ups of tube furnace of nitrogen atmosphere protection, shredded using scissors.After shredding
Carbonization cotton presses 9 with binding agent Kynoar (PVDF):1 ratio mixing, 10h is to uniform for stirring, then will using scraper
It is coated on Copper Foil, 80 DEG C of vacuum drying.After drying, the negative pole after coating is punched into the sequin of a diameter of 18mm, will
It is put on button cell electrode shell, is lithium piece to electrode, and electrolyte uses 1M LiTFSI/DME:DOL(1:1v/v), every
Film is Cegard 2340, is assembled into half-cell.
This half-cell is in 1mA/cm2Discharge and recharge is carried out under constant current density, the embedding lithium of the negative pole for having prepared first is allowed, battery electricity
After pressure reaches 0V, then the constant current lithium ion deposition for carrying out certain hour.After circulation 50 times, negative pole occurs without obvious Li dendrite,
Coulombic efficiency is maintained at 94% or so.
Electrolyte uses 1M LiTFSI/DME simultaneously:DOL(1:1v/v), 0.2M KNO3During for additive, half-cell
Coulombic efficiency reaches more than 99%, and lithium deposition specific discharge capacity reaches 2600mAh/g, and area specific capacity reaches 7mAh/cm2。
Embodiment 2
A certain amount of commercialization carbon felt is taken, is shredded with scissors.Carbon felt and binding agent Kynoar after shredding
(PVDF) 9 are pressed:1 mass ratio mixing, 10h is to uniform for stirring, is then coated onto on Copper Foil using scraper, 80 DEG C of vacuum
Dry.After drying, the negative pole after coating is punched into the sequin of a diameter of 18mm, puts it into button cell electrode shell
On, it is lithium piece to electrode, electrolyte uses 1M LiTFSI/DME:DOL(1:1v/v), barrier film is Cegard 2340, is assembled into
Half-cell.
This half-cell is in 1mA/cm2Discharge and recharge is carried out under constant current density, the embedding lithium of the negative pole for having prepared first is allowed, battery electricity
After pressure reaches 0V, then the constant current lithium ion deposition for carrying out certain hour.After circulation 50 times, negative pole occurs without obvious Li dendrite,
Coulombic efficiency is maintained at 94% or so.Lithium deposition specific discharge capacity reaches 1100mAh/g, and area specific capacity reaches 4mAh/
cm2。
Embodiment 3
A certain amount of commercialization polyimides carbonising carbon fibre is taken, is shredded with scissors.Carbon fiber after shredding and hard carbon,
Binding agent Kynoar (PVDF) presses 6:3:1 mass ratio mixing, 10h is to uniform for stirring, is then applied using scraper
Overlay on Copper Foil, 80 DEG C of vacuum drying.After drying, the negative pole after coating is punched into the sequin of a diameter of 18mm, is put
Enter onto button cell electrode shell, be lithium piece to electrode, electrolyte uses 1M LiTFSI/DME:DOL(1:1v/v), barrier film is
Cegard 2340, is assembled into half-cell.
This half-cell is in 1mA/cm2Discharge and recharge is carried out under constant current density, the embedding lithium of the negative pole for having prepared first is allowed, battery electricity
After pressure reaches 0V, then the constant current lithium ion deposition for carrying out certain hour.After circulation 50 times, negative pole occurs without obvious Li dendrite,
Coulombic efficiency is maintained at 92% or so.Lithium deposition specific discharge capacity reaches 900mAh/g, and area specific capacity reaches 3.5mAh/
cm2。
Embodiment 4
Using the carbonization cotton carbon fiber shredded in embodiment 1, by carbonization cotton carbon fiber, conductive carbon, Kynoar
By 7:2:1 ratio uniform mixing be coated on Copper Foil dry be obtained negative pole, wherein conductive carbon be respectively acetylene black, conductive black,
Electrically conductive graphite, Ketjen black.This four kinds of negative poles constitute half-cell and are tested with lithium piece respectively, and electrolyte is 1M LiTFSI/DME:
DOL(1:1v/v), current density is 1mA/cm2。
Test result shows, in cyclic process, the half-cell that four kinds of different negative poles are constituted, in the interior coulombic efficiency of 50 circles all
More than 96%, produced without obvious dendrite.
Embodiment 5
Using the commercialized carbon fiber of different length, length is respectively 50 microns, 270 microns, 1000 microns, and carbon is fine
Dimension, acetylene black, Kynoar press 5:4:1 ratio uniform mixing is coated on Copper Foil to dry and negative pole is obtained, this three kinds of negative poles point
Do not constitute half-cell with lithium piece to be tested, electrolyte is 1M LiTFSI/DME:DOL(1:1v/v), current density is 1mA/
cm2。
Test result shows, in cyclic process, the half-cell that three kinds of different negative poles are constituted, in the interior coulombic efficiency of 50 circles all
More than 97%, produced without obvious dendrite.
Embodiment 6
Using the commercialized carbon fiber of different-diameter, diameter is respectively 3 microns, 7 microns, 10 microns, by carbon fiber, acetylene
Black, Kynoar presses 8:1:1 ratio uniform mixing be coated on Copper Foil dry be obtained negative pole, this three kinds of negative poles respectively with lithium piece
Constitute half-cell to be tested, electrolyte is 1M LiTFSI/DME:
DOL(1:1v/v), current density is 1mA/cm2。
Test result shows, in cyclic process, the half-cell that three kinds of different negative poles are constituted, in the interior coulombic efficiency of 50 circles all
More than 95%, produced without obvious dendrite.
Embodiment 7
Using the preparation method of carbon fiber in embodiment 1/Copper Foil negative pole, by controlling control during coating to slurry thickness
System, it is 100 microns, 300 microns, 500 microns of carbon fiber/Copper Foil negative pole that thickness is prepared respectively, this three kinds of negative poles respectively with
Lithium piece is assembled into half-cell and is tested, and electrolyte is 1M LiTFSI/DME:DOL(1:1v/v), current density is 1mA/cm2。
Test result shows, in cyclic process, the half-cell that three kinds of different negative poles are constituted, in the interior coulombic efficiency of 50 circles all
More than 96%, produced without obvious dendrite.
Embodiment 8
Using the preparation method of carbon felt carbon fiber/Copper Foil negative pole in embodiment 2, the carbon that porosity is 92% is prepared fine
Dimension/Copper Foil negative pole.In order to prepare lithium/carbon fiber/Copper Foil composite negative pole, placing thickness in carbon fiber/Copper Foil negative terminal surface is
The lithium paper tinsel of 0.1mm, constitutes lithium/carbon fiber/Copper Foil composite negative pole, and stainless steel substrates are used to electrode, and electrolyte is 1M LiTFSI/
DME:DOL(1:1v/v), current density is 1mA/cm2.Method of testing is：First the lithium of negative pole all is deviate to deposit to positive pole
Stainless steel substrates on, the lithium of positive pole is then deposited into negative pole according to a certain amount within a certain period of time, deposit to the lithium of negative pole
Area specific capacity is 4mAh/cm2。
Test result shows, in cyclic process, prepared lithium/carbon fiber composite negative pole and the half of stainless steel substrates composition
Battery, coulombic efficiency is produced all more than 96% without obvious dendrite in 50 circles.
Embodiment 9
The carbon felt carbon fiber and acetylene black that to shred, different binding agents prepare carbon fiber/copper according to different ratios
Paper tinsel negative pole, species and the ratio such as table 1 of binding agent.Carbon fiber/Copper Foil the negative pole that will be prepared constitutes half-cell with lithium piece respectively
Tested, electrolyte is 1M LiTFSI/DME:DOL(1:1v/v), current density is 1mA/cm2, the area specific capacity of deposition
It is 4mAh/cm2。
Test result shows, in cyclic process, prepared by variety classes and different proportion binding agent and carbon fiber
The half-cell that carbon fiber/Copper Foil negative pole is constituted with lithium piece, the coulombic efficiency (table 1) all more than 95% in 50 circles, without obvious branch
Crystalline substance is produced.
The species and ratio of binding agent in carbon fiber/Copper Foil negative pole that table 1 is prepared for the present invention
Embodiment 10
Using prepared carbon fiber/Copper Foil negative pole in embodiment 4, conductive carbon uses carbon black, is constituted with lithium piece
In half-cell, using the solvent (table 2) of the electrolyte and different proportion of variety classes and various concentrations, the electric current of half-cell is close
It is 1mA/cm to spend2, the area specific capacity of deposition is 4mAh/cm2。
Test result shows, in cyclic process, using variety classes and the electrolyte and different proportion of various concentrations
Solvent, half-cell 50 circle in coulombic efficiency (table 2) all more than 97%, without obvious dendrite produce.
The Arrays Aluminum Films in Acid Solution that negative pole prepared by the present invention of table 2 is used
| Lithium salts title | Lithium salt | The ratio of solvent | Coulombic efficiency in 50 circles of half-cell |
| LiTFSI | 0.5M | DME:DOL=1:1 | 97% |
| LiTFSI | 2M | DME:DOL=1:1 | 98% |
| LiTFSI | 5M | DME:DOL=1:1 | 99% |
| LiFSI | 1M | DME:DOL=1:1 | 97% |
| LiTFSI | 2M | DME:DOL=1:2 | 97% |
| LiTFSI | 2M | DME:DOL=2:1 | 97% |
Embodiment 11
Using in embodiment 2 prepare carbon fiber/Copper Foil negative pole, by electrochemical deposition lithium, be prepared into lithium/carbon fiber/
Copper Foil composite negative pole, as the negative pole of lithium-sulfur cell；And positive pole presses 7 by sulphur carbon complex and carbon black, PVDF binding agents:2:1
Mass ratio is prepared into slurry, is coated on aluminium foil, and drying obtains lithium-sulphur cell positive electrode, and the current density of battery is 100mA/g, electricity
Solution liquid uses 1M LiTFSI/DME:DOL(1:1v/v), 0.2M KNO3Used as electrolysis additive, barrier film is Cegard
2340。
Test result shows that after being circulated at 50 times, negative pole is produced without obvious dendrite, and the capacitance loss rate of battery is 25%.
Embodiment 12
It is the foamy carbon that 1mm, porosity are that 95%, aperture is 27 microns to use thickness, and foamy carbon and Copper Foil are overlapped,
Lithium paper tinsel is pressed from both sides between foamy carbon and barrier film to constitute lithium/foamy carbon/Copper Foil composite negative pole.Stainless steel substrates, electrolyte are used to electrode
It is 1M LiTFSI/DME:DOL(1:1v/v), current density is 1mA/cm2.Method of testing is：It is first that the lithium of negative pole is all de-
Go out to deposit on the stainless steel substrates of positive pole, the lithium of positive pole is then deposited into negative pole according to a certain amount within a certain period of time, sink
The lithium area specific capacity that product arrives negative pole is 4mAh/cm2。
Test result shows, in cyclic process, the half-cell that lithium/foamy carbon/Copper Foil is constituted with stainless steel substrates, 100
Coulombic efficiency is produced all more than 96% without obvious dendrite in circle.
Embodiment 13
It is the foamy carbon that 1mm, porosity are that 95%, aperture is 27 microns to use thickness, and foamy carbon and Copper Foil are overlapped, and is obtained
To foamy carbon/Copper Foil composite negative pole, lithium/foamy carbon/Copper Foil combination electrode is then prepared by electrochemical intercalation and deposition,
It is used as lithium-sulfur cell negative pole.And positive pole presses 7 by sulphur carbon complex and carbon black, PVDF binding agents:2:1 mass ratio is prepared into slurry
Material, is coated on aluminium foil, and drying obtains lithium-sulphur cell positive electrode, and the current density of battery is 100mA/g, and electrolyte uses 1M
LiTFSI/DME:DOL(1:1v/v), 0.2M LiNO3Used as electrolysis additive, barrier film is Cegard 2340.
Test result shows that after being circulated at 50 times, negative pole is produced without obvious dendrite, and the capacitance loss rate of battery is 23%.
Embodiment 14
It is the porous carbon fiber paper of 0.5mm to use thickness, and 1 layer of porous carbon fiber paper and Copper Foil are overlapped, fine in porous carbon
Lithium paper tinsel is pressed from both sides between dimension paper and Copper Foil to constitute lithium/carbon fiber paper/Copper Foil composite negative pole.It is that half-cell is constituted to electrode with lithium piece,
Electrolyte is 1M LiTFSI/DME:DOL(1:1v/v), current density is 1mA/cm2。
Test result shows, in cyclic process, the half-cell that lithium/carbon fiber paper/Copper Foil is constituted with lithium piece, in 80 circles
Coulombic efficiency is produced all more than 94% without obvious dendrite.
Comparative example 1
Using thickness be 9mm Copper Foils as lithium deposition substrate, the circular pole piece of a diameter of 18mm is cut out using slicer, by it
Put into as lithium ion deposition substrate on the anode cover of button cell 2032, electrolyte uses 1M LiTFSI/DME:DOL(1:
1v/v), barrier film is Cegard 2340, is lithium piece to electrode.When lithium deposition current is 1mA/cm2, area specific capacity is 1mAh/
cm2, the coulombic efficiency of half-cell just occurs unstable from the beginning, and coulombic efficiency is only 60% or so.
Comparative example 2
Activated carbon YP50F is pressed 9 with Kynoar (PVDF) respectively with commercialization graphite cathode:1 mass ratio mixing,
Used as solvent, copper sheet is coated onto preparing negative pole pole on Copper Foil 1-METHYLPYRROLIDONE (NMP) as collector using scraper
Piece, drying is taken out, and the circular pole piece of a diameter of 18mm is prepared using slicer.Put it into the positive pole of button cell 2032
As Lithium-ion embeding and deposition substrate on shell, electrolyte uses 1M LiTFSI/DME:DOL(1:1v/v), barrier film is Cegard
2340, lithium piece is to electrode.This half-cell is in 1mA/cm2Discharge and recharge is carried out under constant current density, the embedding lithium of activated carbon pole piece is first allowed,
Cell voltage drops to after 0V, is deposited in the constant current lithium ion for carrying out certain hour.Activated carbon negative electrode lithium deposition quality
Specific capacity reaches 1000mAh/g, and area specific capacity reaches 4mAh/cm2, in cycle-index 30 times, coulombic efficiency is maintained at 89%
Left and right, but coulombic efficiency starts unstable after being circulated at 30 times, is merely retained in 80% or so.And graphite cathode is commercialized when lithium is heavy
When product specific discharge capacity reaches 1000mAh/g, half-cell coulombic efficiency is merely retained in less than 80% in preceding 10 circulations, and is surveying
The later stage of examination is also merely retained in 80% or so.
Comparative example 3
Lithium piece as lithium-sulfur cell negative pole；And positive pole presses 7 by sulphur carbon complex and carbon black, PVDF binding agents:2:1 matter
Amount ratio is prepared into slurry, is coated on aluminium foil, and drying obtains lithium-sulphur cell positive electrode, and the current density of battery is 100mA/g, electrolysis
Liquid uses 1M LiTFSI/DME:DOL(1:1v/v), 0.2M KNO3Used as electrolysis additive, barrier film is Cegard 2340.
Test result shows that after 50 this circulation, negative pole has dendrite to produce, and the capacitance loss rate of battery is 35%.
Claims (10)
1. a kind of lithium/carbon fiber or the preparation method of porous carbon paper/Copper Foil composite negative pole for lithium-sulfur cell, its feature exists
In：
Carbon fiber and conductive carbon, binding agent are prepared into carbon fiber/Copper Foil negative pole, the carbon fiber/Copper Foil negative pole by rubbing method
It is embedded in by electrochemical method and lithium deposition, obtains lithium/carbon fiber/Copper Foil composite negative pole；
Or,
Copper Foil and porous carbon quires are closed and prepares porous carbon paper/Copper Foil negative pole, the porous carbon paper/Copper Foil negative pole passes through electrochemistry
Method is embedded in and lithium deposition, obtains lithium/porous carbon paper/Copper Foil composite negative pole.
2. a kind of lithium/carbon fiber or porous carbon paper/Copper Foil composite negative pole for lithium-sulfur cell according to claim 1
Preparation method, it is characterised in that：The mass percentage content of each active component is in the carbon fiber/Copper Foil negative pole：
Binding agent 1%~20%；
Carbon fiber 5%~99%；
Conductive carbon 0%~90%.
3. a kind of lithium/carbon fiber or porous carbon paper/Copper Foil composite negative pole for lithium-sulfur cell according to claim 2
Preparation method, it is characterised in that：The carbon fiber diameter is 0.5 μm~50 μm, length is 1 μm~5000 μm；The carbon fiber
Including at least one of biomass cracking carbon fiber, organic cracking carbon fiber, catalytic pyrolysis.
4. a kind of lithium/carbon fiber or porous carbon paper/Copper Foil composite negative pole for lithium-sulfur cell according to claim 2
Preparation method, it is characterised in that：The binding agent includes Kynoar, Sodium Polyacrylate, polytetrafluoroethylene (PTFE), carboxymethyl cellulose
At least one of plain sodium, sodium alginate, polyvinyl alcohol.
5. a kind of lithium/carbon fiber or porous carbon paper/Copper Foil composite negative pole for lithium-sulfur cell according to claim 2
Preparation method, it is characterised in that：The conductive carbon include acetylene black, conductive black, electrically conductive graphite, Ketjen black, hard carbon at least
It is a kind of；The conductive carbon pattern is mainly particle of the diameter in 1 micron~100 micrometer ranges.
6. a kind of lithium/carbon fiber or porous carbon paper/Copper Foil for lithium-sulfur cell according to any one of Claims 1 to 5
The preparation method of composite negative pole, it is characterised in that：The porosity of copper foil surface material is 20% in the carbon fiber/Copper Foil negative pole
~99%, aperture be 1 micron~5000 microns, thickness be 50 microns~1000 microns.
7. a kind of lithium/carbon fiber or porous carbon paper/Copper Foil for lithium-sulfur cell according to any one of Claims 1 to 5
The preparation method of composite negative pole, it is characterised in that：
With the carbon fiber/Copper Foil negative pole as working electrode, lithium piece is, to electrode, using ethers electrolyte, to be passed through constant current, right
The working electrode is embedded in and lithium deposition, obtains lithium/carbon fiber/Copper Foil composite negative pole；
Or,
With the carbon fiber/Copper Foil negative pole as working electrode, battery is assembled into lithium sulphur positive pole, lithium paper tinsel, barrier film and electrolyte, institute
State lithium paper tinsel to be clipped between the working electrode and barrier film, the battery is once discharged and charging operations, to the work
Electrode is embedded in and lithium deposition, obtains lithium/carbon fiber/Copper Foil composite negative pole；
Or,
With porous carbon paper/Copper Foil negative pole as working electrode, lithium piece is, to electrode, using ethers electrolyte, to be passed through constant current, to institute
State working electrode to be embedded in and lithium deposition, obtain lithium/porous carbon paper/Copper Foil composite negative pole；
Or,
With porous carbon paper/Copper Foil negative pole as working electrode, battery is assembled into lithium sulphur positive pole, lithium paper tinsel, barrier film and electrolyte, it is described
Lithium paper tinsel is clipped between the working electrode and barrier film or is clipped between the porous carbon paper of the working electrode and Copper Foil, by the electricity
Pond is once discharged and charging operations, the working electrode is embedded in and lithium deposition, obtains lithium/porous carbon paper/Copper Foil
Composite negative pole.
8. a kind of lithium/carbon fiber or porous carbon paper/Copper Foil composite negative pole for lithium-sulfur cell according to claim 7
Preparation method, it is characterised in that：The porous carbon paper includes foam carbon paper or porous carbon fiber paper；The hole of the porous carbon paper
Rate is that 20%~99%, aperture is 10 nanometers~5000 microns.
9. a kind of lithium/carbon fiber or porous carbon paper/Copper Foil composite negative pole for lithium-sulfur cell according to claim 7
Preparation method, it is characterised in that：The ethers electrolyte includes lithium salts solute, solvent and additive；
The lithium salts solute is made up of double trifluoromethanesulfonimide lithiums and/or double (fluoro sulphonyl) imine lithiums；
The solvent is made up of glycol dimethyl ether and 1,3- dioxolanes；
The additive is made up of at least one of lithium nitrate, potassium nitrate, rubidium nitrate, cesium nitrate.
10. a kind of lithium/carbon fiber or porous carbon paper/Copper Foil composite negative pole for lithium-sulfur cell according to claim 9
Preparation method, it is characterised in that：The concentration of lithium salts solute is 0.5~5M in the ethers electrolyte, and the solvent is by second two
Diethylene glycol dimethyl ether and 1,3- dioxolanes are by volume (0.5~2):1 composition, the concentration of the additive for 0.01mol/L~
0.4mol/L。
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