CN108321432A - It is a kind of to be used to inhibit carbon nitrogen polymer reference solid state electrolyte of lithium dendrite growth and its preparation method and application - Google Patents
It is a kind of to be used to inhibit carbon nitrogen polymer reference solid state electrolyte of lithium dendrite growth and its preparation method and application Download PDFInfo
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
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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
- 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
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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
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- H01M2300/0017—Non-aqueous electrolytes
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- H01M2300/0082—Organic polymers
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Abstract
The present invention relates to a kind of carbon nitrogen polymer reference solid state electrolyte and its preparation method and application for inhibiting lithium dendrite growth, which includes electrolyte and electrolyte filler, and the electrolyte filler is lightweight carbon nitrogen polymer.A kind of quasi-solid electrolyte that can effectively inhibit the growth of Li dendrite in lithium metal battery is prepared using lightweight carbon nitrogen polymer as electrolyte filler in the present invention.Wherein lightweight carbon nitrogen polymer has pleasantly surprised layered structure, is conducive to the absorption of electrolyte, to form the quasi-solid electrolyte of pureed, can be used for inhibiting the growth of cathode of lithium dendrite in lithium metal battery.
Description
Technical field
It is the invention belongs to field of new energy technologies, more particularly to a kind of for inhibiting the lightweight carbon nitrogen of lithium dendrite growth to polymerize
Object reference solid state electrolyte and its preparation method and application.
Background technology
With Li-S and Li-O2For representative lithium metal battery due to than lithium ion battery have higher energy density and by
Pay attention to extensive.Negative metal lithium is this kind of high power capacity conversion due to low voltage, high theoretical specific capacity (3860mAh/g)
The optimal candidate of reaction cell system.However, in electrochemistry cyclic process, it is non-uniform heavy that lithium metal occurs in negative terminal surface
Product/stripping, the deterioration of battery performance for leading to lithium dendrite growth and its bringing, Li dendrite even can penetrate diaphragm and lead
Cause battery short circuit.In recent years, a variety of strategies are attempted for improving lithium deposition process, inhibit lithium dendrite growth.Such as by lithium metal
Melt and penetrate into the conductive frame matrix with close lithium surface, constructs the small flexible metal cathode of lithium of volume change, in this way
Li dendrite can be eliminated.Collector by building 3-D nano, structure can improve lithium to replace two-dimensional load lithium plane
The depositing behavior of metal, to avoid the growth of Li dendrite.Intrinsic attribute, concentration or the introducing electrolyte for changing electrolyte add
Agent is added also to be important strategy, such as the fluorine sulfimide radical ion (FSI based on ionic liquid or high concentration-) can be effectively ensured
The lithium deposition process of lithium metal battery high magnification, stabilization, FSI-It can be in lithium metal surface reduction (mainly generating LiF), shape in situ
At firm solid electrolyte boundary layer (SEI), and then ensure not will produce Li dendrite in lithium metal deposition process.For Li-S
Battery system, synergistic effect can be generated by being added while the polysulfide and lithium nitrate of lithium, SEI be reinforced, to protect cathode of lithium
From corrosion.Lithium gold also can effectively be ensured for the modification (such as introducing polar functional group on membrane fibers surface) of diaphragm
Belong to the uniform deposition in cathode.
Compared to the electrolyte that additive is reinforced, solid-state or quasi-solid electrolyte have better mechanical strength, by the phase
Prestige has better inhibiting effect to Li dendrite.However the usual conductivity of all solid state electrolyte is inadequate, poor interfacial contact problem
Also it is difficult to solve.Quasi-solid electrolyte has the conductivity similar with electrolyte and good interface wetting power, is considered
It is one of the optimal candidate of novel lithium metal cell electrolyte.Quasi-solid electrolyte often adds non-aqueous electrolyte or lithium salts
Enter polymer backbone (such as polyethylene glycol oxide) or inorganic nanoparticles (such as nano silicon dioxide) filler cures.Electrolysis
The quasi- solid state of matter not but not causes the significant decrease of conductivity due to space charge effect, instead may be used in some cases
Its conductivity can be increased.However, the mechanical strength of traditional polymer film based on polyethylene glycol oxide is weaker, cannot effectively inhibit
Li dendrite, it is often necessary to which adding inorganic nano particle is improved.
Invention content
In view of the above-mentioned problems, the purpose of the present invention is to provide a kind of new polymers reference solid state electricity of high mechanical properties
Solve matter and its preparation method and application.
On the one hand, the present invention provides a kind of for inhibiting the lightweight carbon nitrogen polymer reference solid state of lithium dendrite growth to be electrolysed
Matter (the carbon nitrogen polymer reference solid state electrolyte for inhibiting lithium dendrite growth), including electrolyte and electrolyte filler, institute
It is lightweight carbon nitrogen polymer to state electrolyte filler.
For the present invention using lightweight carbon nitrogen polymer as electrolyte filler, being prepared a kind of can effectively inhibit lithium metal battery
The quasi-solid electrolyte of the growth of middle Li dendrite.Wherein lightweight carbon nitrogen polymer has pleasantly surprised layered structure, is conducive to be electrolysed
The absorption of liquid can be used for inhibiting the growth of cathode of lithium dendrite in lithium metal battery to form the quasi-solid electrolyte of pureed.It is poly-
Close object g-C3N4There is high mechanical strength, the closs packing of layered structure mechanical strength to be made to further enhance for itself, therefore as electricity
Solve liquid filler, g-C3N4The growth of Li dendrite can effectively be inhibited.When the lightweight carbon nitrogen polymer reference solid state electrolyte and lithium
When metal negative electrode contacts, which also has the interface impedance with the same order of magnitude of conventional electrolysis liquid, and good
Interfacial adhesion.And during the long circulating of lithium metal Symmetrical cells, which can greatly slow down lithium
The increase of voltage polarizing in metal deposit/stripping process, enhances the cyclical stability of battery.
Preferably, the lightweight carbon nitrogen polymer includes the three-dimensional meso-hole ball g-C of self assembly3N4, two-dimensional nano thin layer g-
C3N4, oxygen doping stripping lack layer O-g-C3N4, S doping S-g-C3N4At least one of.
In the lightweight carbon nitrogen polymer reference solid state electrolyte mass percent of lightweight carbon nitrogen polymer be 20~
25wt%.
Preferably, the electrolyte includes solute and solvent, the solute is bis-trifluoromethylsulfoandimide lithium LiTFSI, six
Lithium fluophosphate LiPF6, lithium perchlorate LiClO4, at least one of double fluorine sulfimide lithium LiFSI；The solvent is diethylene glycol (DEG)
The double trifluoromethanesulfonimides of dimethyl ether DGM, triethylene glycol dimethyl ether TEGDME, -3 methyl of ionic liquid 1- ethyls
At least one of EmimTFSI, ethylene carbonate EC and dimethyl carbonate DMC；Solute is a concentration of in the electrolyte
0.5~1.5mol/L.
Also, preferably, the diethylene glycol dimethyl ether DGM that it is bis-trifluoromethylsulfoandimide lithium LiTFSI that the electrolyte, which is solute,
The triethylene glycol dimethyl ether TEGDME solution or solute that solution, solute are LiTFSI are lithium hexafluoro phosphate LiPF6Volume ratio be
1:1 ethylene carbonate EC and dimethyl carbonate DMC solution；A concentration of 0.5~1.5mol/L of solute in the electrolyte.
It on the other hand, will be light the present invention provides a kind of lightweight carbon nitrogen polymer reference solid state electrolyte preparation method
Matter carbon nitrogen polymer is sufficiently mixed with electrolyte, obtains the lightweight carbon nitrogen polymer reference solid state electrolyte.
Preferably, the particle diameter distribution of the lightweight carbon nitrogen polymer is 3.5~8 μm.The lightweight carbon nitrogen polymer is to receive
When rice structure, easily mud is mixed into electrolyte, it is ensured that this easy moulding process of quasi-solid electrolyte.
The third aspect, the present invention also provides a kind of lithium metals pair based on lightweight carbon nitrogen polymer reference solid state electrolyte
Battery system, the lithium metal Symmetrical cells system is claimed to include lightweight carbon nitrogen polymer reference solid state electrolyte and be located at light
The metal lithium sheet of matter carbon nitrogen polymer reference solid state electrolyte both sides.
When the lightweight carbon nitrogen polymer reference solid state electrolyte is used for lithium metal Symmetrical cells, with good boundary
Face stability and low interface impedance, the voltage polarizing reduced in lithium metal deposition/stripping process is poor, enhances Symmetrical cells
Cyclical stability, the metallic lithium surface after Symmetrical cells long circulating is still smooth fine and close.
Fourth aspect, the present invention also provides a kind of lithium metal battery include anode, cathode and positioned at it is described just
Lightweight carbon nitrogen polymer reference solid state electrolyte between pole and cathode, the cathode are metal lithium sheet, the just extremely FeS2、
Carbon-sulfur compound, LiFePO4、LiMn2O4、LiCoO2, rich at least one of nickel ternary system and rich lithium manganese base solid solution.
Preferably, the anode is preferably FeS2.When the lightweight carbon nitrogen polymer reference solid state electrolyte is used for Li-
FeS2When lithium metal battery, which improve the patterns of cathode of lithium, weaken the shuttle effect of polysulfide, it is ensured that are more than 400
The battery long-life of secondary cycle.
The present invention has following positive effect.
(1) electrolyte filler of the present invention using lightweight carbon nitrogen polymer as quasi-solid electrolyte, it was confirmed that its conduct
The superiority of electrolyte filler.Such as in spherical g-C3N4Building-up process in, a large amount of thin layer nanometer sheet self assembly is gathered into
Even Mesoporous Spheres, this fine layered structure are conducive to the absorption of electrolyte, at the same the powder of nanostructure easily with electrolysis
Liquid is mixed into mud, it is ensured that this easy moulding process of quasi-solid electrolyte.
(2) spherical g-C in the present invention3N4With the uniform purees that electrolyte is mixed into can be effectively adhered lithium metal or
The interface impedance of electrode material surface, quasi-solid electrolyte and lithium anode is easier than the interface impedance of pure electrolyte system
Reach stable, the former transfer impedance in interface can be down to 115 Ω cm2, spread in the interface of 30 to 70 DEG C of temperature ranges
Activation energy is 0.45eV.
(3) present invention in quasi-solid electrolyte be used for lithium metal Symmetrical cells when, significantly reduce lithium metal it is reversible deposition/
Polarization potential in stripping process is poor, and enhances the cyclical stability of Symmetrical cells.Lithium metal based on quasi-solid electrolyte
Deposition/stripping that Symmetrical cells are stablized has benefited from inhibition of the electrolyte to lithium dendrite growth.
(4) lightweight carbon nitrogen polymer reference solid state electrolyte is used for Li-FeS in the present invention2When lithium metal battery, due to lithium
Dendrite is suppressed, and to which cathode of lithium pattern is significantly improved, which can also weaken the shuttle effect of polysulfide,
It is ensured that Li-FeS2Battery is more than the long-life of 400 cycles.
The method of the invention production technology is easy, is suitble to large-scale application, has to the development of lithium metal battery important
Meaning.
Description of the drawings
Fig. 1 is the g-C of three-dimensional meso-hole spherical particle composition3N4XRD diagram；
Fig. 2 is the g-C of three-dimensional meso-hole spherical particle composition3N4SEM figure；
Fig. 3 is based on g-C3N4The interface AC impedance figure of the Temporal Evolution of the lithium metal Symmetrical cells of quasi-solid electrolyte
Spectrum is inserted into figure：Interface impedance value changes with time；
Fig. 4 is based on g-C3N4The alternating temperature ac impedance spectroscopy of the lithium metal Symmetrical cells of quasi-solid electrolyte；
Fig. 5 is based on g-C3N4The lithium metal Symmetrical cells of the quasi-solid electrolyte Allan Buddhist nun that impedance value derives at different temperatures
This black point diagram；
Fig. 6 is based on g-C3N4Quasi-solid electrolyte or based on the lithium metal Symmetrical cells of pure electrolyte in 0.5mA/cm2When lithium
The potential curve figure of metal deposit/strip cycles is inserted into figure：The potential curve amplified under particular cycle number compares；
Fig. 7 is based on g-C3N4Quasi-solid electrolyte or based on the lithium metal Symmetrical cells of pure electrolyte in 2mA/cm2When lithium gold
Belong to the potential curve figure of deposition/strip cycles, is inserted into figure：The potential curve amplified under particular cycle number compares；
Fig. 8 is based on g-C3N4The lithium metal Symmetrical cells of quasi-solid electrolyte are in 2mA/cm2When, lithium metal deposits/remove 120
SEM surface topography maps after secondary cycle；
Fig. 9 is based on g-C3N4The Li-FeS of quasi-solid electrolyte2The charging and discharging curve figure of 200 cycles before battery；
Figure 10 is based on O-g-C3N4The interface AC impedance of the Temporal Evolution of the lithium metal Symmetrical cells of quasi-solid electrolyte
Collection of illustrative plates is inserted into figure：Interface impedance value changes with time；
Figure 11 is based on O-g-C3N4The lithium metal Symmetrical cells of quasi-solid electrolyte are in 0.5 and 2mA/cm2When lithium metal it is heavy
The potential curve figure of product/strip cycles.
Specific implementation mode
It is further illustrated the present invention below by way of following embodiments, it should be appreciated that following embodiments are merely to illustrate this
Invention, is not intended to limit the present invention.
The present invention adds a kind of nanostructured polymers filler with high mechanical properties in the electrolytic solution, to cure electricity
Liquid is solved, quasi-solid electrolyte is constructed, achievees the purpose that inhibit cathode of lithium dendritic growth in lithium metal battery.Specifically, with light
Matter carbon nitrogen polymer is uniformly mixed as electrolyte filler, with electrolyte, is formed pureed quasi-solid electrolyte, be can be used for inhibiting
The growth of cathode of lithium dendrite in lithium metal battery.Lightweight carbon nitrogen is poly- in the lightweight lightweight carbon nitrogen polymer reference solid state electrolyte
The mass percent for closing object can be 20~25wt%, and content is too high or too low is all difficult to form preferable pureed electrolyte.
The three-dimensional meso-hole ball g-C for self assembly can be selected in upper lightweight carbon nitrogen polymer3N4(brown color), two-dimensional nano thin layer
g-C3N4Layer O-g-C is lacked in the stripping of (glassy yellow), oxygen doping3N4The S-g-C of (white), S doping3N4At least one in (taupe)
Kind.
Lightweight carbon nitrogen polymer reference solid state electrolyte of the present invention, by carbon nitrogen polymer and the uniform mixing of electrolyte
At wherein electrolyte includes solute and solvent.The solute can be bis-trifluoromethylsulfoandimide lithium LiTFSI, lithium hexafluoro phosphate
LiPF6, lithium perchlorate LiClO4, at least one of double fluorine sulfimide lithium LiFSI.The solvent can be diethylene glycol dimethyl ether
The double trifluoromethanesulfonimide EmimTFSI of DGM, triethylene glycol dimethyl ether TEGDME, -3 methyl of ionic liquid 1- ethyls, carbonic acid
At least one of vinyl acetate EC and dimethyl carbonate DMC.The concentration of solute can be 0.5~1.5mol/ in the electrolyte
L.The electrolyte is preferably：Solute be bis-trifluoromethylsulfoandimide lithium (LiTFSI) diethylene glycol dimethyl ether (DGM) solution,
Triethylene glycol dimethyl ether (TEGDME) solution that solute is LiTFSI, solute are lithium hexafluoro phosphate (LiPF6) volume ratio be 1:1
Ethylene carbonate (EC) and dimethyl carbonate (DMC) solution one kind, concentration of electrolyte 0.5-1.5mol/L.
Illustrate to following exemplary lightweight carbon nitrogen polymer reference solid state electrolyte preparation method provided by the invention.
Lightweight carbon nitrogen polymer is sufficiently mixed with electrolyte, obtains the lightweight carbon nitrogen polymer reference solid state electrolysis
Matter.The particle diameter distribution of the lightweight carbon nitrogen polymer can be 3.5~8 μm.As an example, the g-C of 50-150mg is taken3N4Powder
Then the electrolyte of 250-350 μ l is added in agate mortar in last sample, be fully ground uniformly, obtain lightweight carbon nitrogen polymer
Reference solid state electrolyte.The thickness of the lightweight carbon nitrogen polymer reference solid state electrolyte can be adjusted as needed, thick
Degree may generally be 80-120 microns.
Lithium metal Symmetrical cells system provided by the invention refers to the battery that quasi-solid electrolyte bilateral is all metal lithium sheet.
The lithium deposition of the wherein described lithium metal Symmetrical cells system and the current density of strip cycles test can be 0.5-2mA/cm2, often
The time for depositing or removing in secondary cycle can be 1-3 hours.
Lithium metal battery provided by the invention, cathode metal lithium sheet, anode can be FeS2, carbon-sulfur compound,
LiFePO4、LiMn2O4、LiCoO2, rich nickel ternary system, at least one of rich lithium manganese base solid solution, do not need diaphragm, standard is solid
State electrolyte is placed between positive and negative anodes.Since dendrite inhibits, the Li-FeS based on carbon nitrogen polymer2Quasi- solid state battery, which has, to be more than
The long-life of 400 cycles.
The present invention obtains pureed quasi-solid electrolyte, effectively inhibits using lightweight carbon nitrogen polymer as electrolyte filler
The growth of Li dendrite in lithium metal battery.The quasi-solid electrolyte has the interface impedance similar with electrolyte；For lithium gold
When belonging to Symmetrical cells, with good interface stability and low interface impedance, lithium metal deposition/removed is significantly reduced
Voltage polarizing in journey is poor, enhances the cyclical stability of Symmetrical cells, improves the pattern of deposit lithium metal, and Symmetrical cells are long
Metallic lithium surface after cycle is still smooth fine and close.For Li-FeS2When battery, the shuttle effect of polysulfide is weakened, is shown
Write the decaying for slowing down battery capacity, it is ensured that battery is more than the long-life of 400 cycles.
Embodiment is enumerated further below so that the present invention will be described in detail.It will similarly be understood that following embodiment is served only for this
Invention is further described, and should not be understood as limiting the scope of the invention, those skilled in the art is according to this hair
Some nonessential modifications and adaptations that bright the above is made all belong to the scope of protection of the present invention.Following examples are specific
Technological parameter etc. is also only an example in OK range, i.e. those skilled in the art can be done properly by the explanation of this paper
In the range of select, and do not really want to be defined in hereafter exemplary concrete numerical value.
Embodiment 1
1) mesoporous spherical g-C3N4Preparation
Melamine 1.9977g is weighed, is dissolved in the dimethyl sulfoxide (DMSO) (DMSO) of 80mL；Take the cyanuric acid of equimolar amounts
(2.0446g) is dissolved in the dimethyl sulfoxide (DMSO) of 40mL.It stirs at each comfortable 60 DEG C of two kinds of solution, after uniform dissolution, is mutually mixed,
It is maintained at 60 DEG C and stirs 10 minutes again, be then allowed to stand to room temperature.After mixed liquor is centrifuged, is washed 5 times with ethyl alcohol, be placed in 50 DEG C
Vacuum drying chamber in it is dry, obtain white powder.White powder is put into ceramic crucible, is placed in tube furnace, high-purity
In the atmosphere of argon gas, 550 DEG C are risen to the heating rate of 2.3 DEG C/min, is sintered 4 hours, obtains pale brown sample powder.Its
XRD is as shown in Figure 1, diffraction maximum corresponds to the g-C of nanostructure3N4Pure phase.g-C3N4SEM it is as shown in Figure 2, it can be seen that g-C3N4
It is made of the spherical particle of about 5 microns of sizes, each particle has a large amount of thin layer nanometer sheet self assembly to assemble again, therefore table
Reveal porous pattern.
2) preparation of electrolyte
The preparation of electrolyte is carried out in the argon gas glove box of water number, oxygen value less than 0.1ppm.By the double of 1.4354g (5mmol)
Fluoroform sulfimide lithium (LiTFSI) is dissolved in the diethylene glycol dimethyl ether (DGM) of 5mL, and then solution is placed in magnetic stirring apparatus
On, it stirs 24 hours, obtains the LiTFSI/DGM electrolyte of 1mol/L.
3) preparation of quasi-solid electrolyte
By obtained g-C in 1)3N4Powder sample is placed in 120 DEG C of vacuum drying oven and is dried in vacuo 24 hours, then shifts
To argon gas glove box.Take the g-C of 100mg3N4Then the LiTFSI/DGM electrolysis of 300 μ l are added in agate mortar in powder sample
Liquid is fully ground uniformly, obtains mesoporous spherical g-C3N4Quasi-solid electrolyte as polymer-filled agent.The lightweight carbon nitrogen
The mass percent of lightweight carbon nitrogen polymer is 20wt% in polymer matrix quasi-solid electrolyte.
4) Integration Assembly And Checkout of lithium metal Symmetrical cells
The assembling of 2032 button cells is carried out in the argon gas glove box of water number, oxygen value less than 0.1ppm.Specifically, diameter is taken
For the metal lithium sheet of 12mm, the 3 of one layer of about 0.1mm are uniformly coated on surface) described in quasi-solid electrolyte after, then it is solid in standard
State bath surface spreads the metal lithium sheet of an a diameter of 10mm, is assembled into button cell.As a comparison, with Celgard be every
The LiTFFSI/DGM electrolyte of 70 μ l is added in film, also similar to be assembled into Symmetrical cells.At room temperature, the friendship of Symmetrical cells is carried out
Flow impedance is tested, and setting bias is 100mV, frequency range 10-2-106Hz.For test lithium metal and quasi-solid electrolyte (or
Celgard loads electrolyte) interface impedance evolution at any time, once tested every 24 hours, up to impedance value does not have
There is apparent fluctuation.Fig. 3 shows that interface impedance changes with time between lithium metal and quasi-solid electrolyte, it can be seen that boundary
Face impedance value is stablized in 115 Ω cm after 48 hrs2Left and right.Then, alternating temperature exchange is carried out to the Symmetrical cells after ambient-temp-stable
Testing impedance, temperature range are 30-70 DEG C, primary every 10 DEG C of tests, 1 hour are kept the temperature in each temperature nodes, really
Protect the stabilization of battery system.Fig. 4 shows exchange resistance of the Symmetrical cells based on quasi-solid electrolyte in 30-70 DEG C of temperature range
Anti- spectrogram can calculate interface Diffusion Activation Energy according to the AC impedance under different temperatures according to Arrhenius equation
It is corresponding Arrhenius point for 0.45eV, Fig. 5.
2032 button Symmetrical cells of assembling are subjected to charge-discharge test on LAND electrochemical workstations, in 0.5mA/
cm2Current density under, first constant-current charge 3 hours, then constant-current discharge 3 hours again, deposition/removed occurs for detection lithium metal
The voltage polarizing of journey is poor, and is unfolded to recycle with this step.Fig. 6 and Fig. 7 is based on Mesoporous Spheres g-C3N4Quasi-solid electrolyte and pure electricity
The cyclic curve of lithium metal deposition/stripping process of the Symmetrical cells of liquid under different current densities is solved, as seen from the figure, standard is solid
The polarization potential that state electrolyte significantly reduces in lithium metal deposition/stripping process is poor, and enhances the cycle of Symmetrical cells
Stability.In 0.5mA/cm2Current density under, after 50 cycles, polarizing voltage difference maintains 50mV or so, and pure electrolyte
After system Symmetrical cells are recycled at 50 times, polarizing voltage difference has been up to 400mV.In up to 2mA/cm2Current density under, still
Keep deposition/splitting time constant (3 hours), the polarizing voltage difference of quasi- solid-state system can still maintain low 100mV or so.
After Symmetrical cells recycle certain number, battery is disassembled in the glove box full of argon gas, takes out metal lithium sheet, be placed in electrolyte
It is cleaned in solvent DGM for several times, naturally dry, is put into scanning electron microscope device under protection of argon gas and carries out morphology observations.Fig. 8
For 2mA/cm2Under current density, the pattern of metallic lithium surface after 120 cycles of quasi-solid electrolyte Symmetrical cells can from figure
To find out, the lithium metal surface after high current density cycle is still smooth fine and close, it was confirmed that cathode lithium dendrite growth is effectively pressed down
System.
5) Li-FeS based on quasi-solid electrolyte2The Integration Assembly And Checkout of battery
a)FeS2The preparation of positive electrode
Weigh business FeS2Powder sample 35mg, Super P 10mg, are put into mortar and grind 30min, and it is dense that PVDF is added later
Degree is the 100 μ l of nmp solution of 20mg/ μ l, grinds 10~15min.It is 50mm that black paste is uniformly applied to area2Aluminium foil
On, and be put into 80 DEG C of vacuum drying ovens and dry 12 hours.The aluminium foil of carrying active substance after vacuum drying is weighed again,
And pack, it is put into glove box；
B) Integration Assembly And Checkout of battery
The assembling of 2032 button cells is carried out in the argon gas glove box of water number, oxygen value less than 0.1ppm.Detailed process is, straight
One layer of above-mentioned quasi-solid electrolyte is uniformly coated in the lithium piece that diameter is 10mm, then by the anode electrode piece of carrying active substance
It is placed on electrolyte, is assembled into Li-FeS2Lithium metal battery.Assembled battery is filled on LAND electrochemical workstations
Discharge test, voltage range 1-3V, current ratio are that (1C corresponds to FeS to 0.1C24 electronics conversion reactions or 892mAh/g
Theoretical specific capacity completed required current density at 1 hour).Fig. 9 is Li-FeS2Battery typically fills in being recycled at first 200 times
Discharge curve, since Li dendrite is suppressed, cathode of lithium pattern is significantly improved, and the polarity of the quasi-solid electrolyte is also beneficial to weak
Change the shuttle effect of polysulfide, therefore ensure that battery is more than the long-life of 400 cycles.
Embodiment 2
1) single layer sheet O-g-C3N4Preparation
The melamine of 4g is placed in Muffle furnace, Muffle furnace and air communication, is warming up to 550 DEG C with the rate of 2 DEG C/min, herein
4 hours of temperature obtain the blocky porous solid sample of glassy yellow.After sample is fully ground into powder, it is placed in burning
In boat, it is warming up to 550 DEG C with the rate of 5 DEG C/min and keeps the temperature 1 hour, obtain faint yellow solid powder.Then again by this powder
It is warming up to 550 DEG C with the rate of 2 DEG C/min and keeps the temperature 1 hour, obtains the final sample of white.Above-mentioned all temperature-rise periods all exist
It is carried out in air atmosphere；
2) configuration of electrolyte
The preparation of electrolyte is carried out in the argon gas glove box of water number, oxygen value less than 0.1ppm.By the double of 1.4354g (5mmol)
Fluoroform sulfimide lithium (LiTFSI) is dissolved in the diethylene glycol dimethyl ether (DGM) of 5mL, and then solution is placed in magnetic stirring apparatus
On, it stirs 24 hours, obtains the LiTFSI/DGM electrolyte of 1mol/L；
3) preparation of quasi-solid electrolyte
By obtained sheet O-g-C in 1)3N4Powder sample, which is placed in 120 DEG C of vacuum drying ovens, is dried in vacuo 24 hours, so
After be transferred to argon gas glove box.Take the O-g-C of 120mg3N4The LiTFSI/DGM of 300 μ l is added in agate mortar in powder sample
Electrolyte is fully ground uniformly, obtains oxygen doping sheet O-g-C3N4Quasi-solid electrolyte as polymer-filled agent.Institute
The mass percent for stating lightweight carbon nitrogen polymer in lightweight carbon nitrogen polymer reference solid state electrolyte is 25wt%；
4) Integration Assembly And Checkout of lithium metal Symmetrical cells
The assembling of 2032 button cells is carried out in the argon gas glove box of water number, oxygen value less than 0.1ppm.Specifically, diameter is taken
For the metal lithium sheet of 12mm, the 3 of one layer of about 0.1mm are uniformly coated on surface) described in quasi-solid electrolyte after, then in standard
It is then covered with the metal lithium sheet of an a diameter of 10mm on solid electrolyte, is assembled into button cell.As a comparison, it is with Celgard
Diaphragm loads the LiTFSI/DGM electrolyte of upper 70 μ l, is also assembled into Symmetrical cells.Interface exchange is carried out to above-mentioned Symmetrical cells
Testing impedance (stability at any time and alternating temperature AC impedance that include interface impedance), and the lithium under different current densities
The charge-discharge test of metal deposit/stripping.Figure 10 is demonstrated by lithium metal and O-g-C3N4Interface impedance between reference solid state electrolyte
It changes with time, it can be seen that interface impedance value is stablized after 168 hours in 550 Ω cm2Left and right.Figure 11, which is shown, to be based on
O-g-C3N4The Symmetrical cells of quasi-solid electrolyte are in 0.5mA/cm2And 2mA/cm2Lithium metal deposition/stripping under current density
The cyclic curve of process, as seen from the figure, low current density can maintain better cyclical stability, the potential pole after 80 cycles
Change remains within 100mV or so.
It is it is necessary to described herein finally：Above example is served only for making technical scheme of the present invention further detailed
It describes in detail bright, should not be understood as limiting the scope of the invention, those skilled in the art's the above according to the present invention
Some the nonessential modifications and adaptations made all belong to the scope of protection of the present invention.
Claims (9)
1. a kind of lightweight carbon nitrogen polymer reference solid state electrolyte for inhibiting lithium dendrite growth, which is characterized in that including electricity
Liquid and electrolyte filler are solved, the electrolyte filler is lightweight carbon nitrogen polymer.
2. lightweight carbon nitrogen polymer reference solid state electrolyte according to claim 1, which is characterized in that the lightweight carbon nitrogen
Polymer includes the three-dimensional meso-hole ball g-C of self assembly3N4, two-dimensional nano thin layer g-C3N4, oxygen doping stripping lack layer O-g-C3N4、
The S-g-C of S doping3N4At least one of.
3. lightweight carbon nitrogen polymer reference solid state electrolyte according to claim 1 or 2, which is characterized in that the lightweight
The mass percent of lightweight carbon nitrogen polymer is 20~25wt% in carbon nitrogen polymer reference solid state electrolyte.
4. lightweight carbon nitrogen polymer reference solid state electrolyte according to any one of claim 1-3, which is characterized in that institute
It includes solute and solvent to state electrolyte, and the solute is bis-trifluoromethylsulfoandimide lithium LiTFSI, lithium hexafluoro phosphate LiPF6, it is high
Lithium chlorate LiClO4, at least one of double fluorine sulfimide lithium LiFSI；The solvent is diethylene glycol dimethyl ether DGM, three second two
The double trifluoromethanesulfonimide EmimTFSI of diethylene glycol dimethyl ether TEGDME, ionic liquid 1- ethyls -3 methyl, ethylene carbonate EC and
At least one of dimethyl carbonate DMC；A concentration of 0.5~1.5 mol/L of solute in the electrolyte.
5. lightweight carbon nitrogen polymer reference solid state electrolyte according to claim 4, which is characterized in that the electrolyte is
The triethylene glycol two that diethylene glycol dimethyl ether DGM solution, the solute that solute is bis-trifluoromethylsulfoandimide lithium LiTFSI are LiTFSI
Methyl ether TEGDME solution or solute are lithium hexafluoro phosphate LiPF6Volume ratio be 1:1 ethylene carbonate EC and dimethyl carbonic acid
Ester DMC solution；A concentration of 0.5~1.5 mol/L of solute in the electrolyte.
6. a kind of lightweight carbon nitrogen polymer reference solid state electrolyte preparation method as described in any one of claim 1-5,
It is characterized in that, lightweight carbon nitrogen polymer is sufficiently mixed with electrolyte, the lightweight carbon nitrogen polymer reference solid state electricity is obtained
Xie Zhi.
7. preparation method according to claim 6, which is characterized in that the particle diameter distribution of the lightweight carbon nitrogen polymer is
3.5~8 μm.
8. a kind of lithium metal Symmetrical cells system based on lightweight carbon nitrogen polymer reference solid state electrolyte, which is characterized in that institute
It includes the lightweight carbon nitrogen polymer reference solid state electrolysis described in any one of claim 1-5 to state lithium metal Symmetrical cells system
Matter and metal lithium sheet positioned at lightweight carbon nitrogen polymer reference solid state electrolyte both sides.
9. a kind of lithium metal battery based on lightweight carbon nitrogen polymer reference solid state electrolyte, which is characterized in that the lithium metal
Battery includes the lightweight carbon described in any one of anode, cathode and claim 1-5 between the anode and cathode
Nitrogen polymer reference solid state electrolyte, the cathode are metal lithium sheet, the just extremely FeS2, carbon-sulfur compound, LiFePO4、
LiMn2O4、LiCoO2, rich at least one of nickel ternary system and rich lithium manganese base solid solution.
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| CN108982471A (en) * | 2018-08-02 | 2018-12-11 | 江苏师范大学 | AgNR/O-g-C3N4Substrate, preparation method and its application in recyclable SERS Sensitive Detection |
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| CN109786870A (en) * | 2018-12-25 | 2019-05-21 | 上海力信能源科技有限责任公司 | A method of it reducing lithium battery and analyses lithium |
| CN109802173A (en) * | 2019-01-24 | 2019-05-24 | 北京化工大学 | A kind of three-phase organic/inorganic plural gel state polymer dielectric and preparation method thereof |
| CN109802173B (en) * | 2019-01-24 | 2021-03-26 | 北京化工大学 | Three-phase organic/inorganic composite gel-state polymer electrolyte and preparation method thereof |
| CN109755640A (en) * | 2019-03-13 | 2019-05-14 | 西安交通大学 | A kind of preparation method of composite solid polymer electrolyte |
| CN114551793A (en) * | 2021-09-18 | 2022-05-27 | 万向一二三股份公司 | Lithium-based composite negative plate with long cycle life, preparation method thereof and solid lithium battery |
| CN114551793B (en) * | 2021-09-18 | 2023-10-03 | 万向一二三股份公司 | Lithium-based composite negative plate with long cycle life, preparation method thereof and solid lithium battery |
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