CN108933047A - A kind of prelithiation gel electrolyte and preparation method thereof for lithium-ion capacitor - Google Patents
A kind of prelithiation gel electrolyte and preparation method thereof for lithium-ion capacitor Download PDFInfo
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- CN108933047A CN108933047A CN201810783395.5A CN201810783395A CN108933047A CN 108933047 A CN108933047 A CN 108933047A CN 201810783395 A CN201810783395 A CN 201810783395A CN 108933047 A CN108933047 A CN 108933047A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/54—Electrolytes
- H01G11/56—Solid electrolytes, e.g. gels; Additives therein
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/04—Hybrid capacitors
- H01G11/06—Hybrid capacitors with one of the electrodes allowing ions to be reversibly doped thereinto, e.g. lithium ion capacitors [LIC]
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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
- 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
- H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
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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
- H01M2300/00—Electrolytes
- H01M2300/0088—Composites
- H01M2300/0091—Composites in the form of mixtures
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- 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
- Y02E60/13—Energy storage using capacitors
Abstract
The invention discloses a kind of preparation methods of prelithiation gel electrolyte for lithium-ion capacitor, belong to electrolyte field.The electrolyte is made of porous polymer polymer in situ fixed ion liquid electrolyte, lithium powder, ionic liquid electrolyte is by ionic liquid and lithium salts, preparation method includes the following steps: (1), disperses high molecular polymer in organic solvent in inert gas environment and obtains mixed system, and heating stirring is uniform；By ionic liquid, lithium salts, lithium powder sequentially adds the mixed system, by solution-cast, is dried in vacuo, ultimately forms gel electrolyte.(2), prelithiation gel electrolyte obtained by step (1) and electrode material are assembled into lithium-ion capacitor.The processing of constant current charge-discharge prelithiation is carried out, the lithium-ion capacitor of prelithiation cathode is obtained.The present invention is combined by the pre- embedding lithium of the pre- embedding lithium of physics and electrochemistry, makes up the microcosmic embedding lithium inhomogeneities by the pre- embedding lithium of physics, is solved the problems, such as that the pre- embedding lithium technique of electrochemistry depth is cumbersome and takes long time, is widened voltage window, improves capacity.
Description
Technical field
The invention belongs to electrochemical energy technical field more particularly to a kind of prelithiation gels for lithium-ion capacitor
Electrolyte and its preparation method and application.
Background technique
21 century, as the sharp increase and economic rapid development, demand of the countries in the world to the energy of population increasingly increase
Add, due to environmental degradation caused by the exhaustion of traditional energy (coal, petroleum, natural gas etc.) and the inefficient utilization of the energy, new energy
Source develops and utilizes an important topic for becoming the world today.Recently as the increasingly mature of new energy development, development is new
Energy storage and conversion equipment become the needs of era development.Chemical energy storage device is the important component in energy system,
Wherein supercapacitor and lithium ion battery are widely paid close attention to and are studied due to haveing excellent performance.
Lithium ion battery is a kind of secondary cell (rechargeable battery), it relies primarily on lithium ion and moves between a positive electrode and a negative electrode
It moves and carrys out work.In charge and discharge process, Li+ insertion and deintercalation back and forth between two electrodes: when charging, Li+ from positive deintercalation,
It is embedded in cathode by electrolyte, cathode is in lithium-rich state；It is then opposite when electric discharge.Lithium ion battery due to high-energy density, by
To being widely applied.However lower power density and cyclical stability restrict its development.
For lithium-ion capacitor as a kind of novel hybrid capacitors, it combines double layer capacitor and lithium ion battery
The advantages of, that is, have many advantages, such as high-power output, high capacity and high circulation service life, is expected in new energy power vehicle, e-mail
The fields such as breath, instrument and meter, aerospace are widely used.The working mechanism of lithium-ion capacitor is as follows: when charging, having
Lithium ion in machine electrolyte, which is embedded into negative electrode material, forms lithium intercalation compound, and the anion in electrolyte is then adsorbed on anode
Surface forms electric double layer；And when discharging, lithium ion is deviate from from negative electrode material, while double electricity that anode is generated with electrolyte interface
Layer dissociation, anion are discharged from positive electrode surface.Lithium-ion capacitor is a kind of safe and environmental-friendly energy storage device.
In lithium-ion capacitor carbon based negative electrodes material electrodes, passivation is formed in negative terminal surface during initial charge
Film.The film inhibits decomposition reaction and the mode being not inserted between carbon negative pole material lattice layer with organic solvent is distributed, and
From there through stablize carbon-based negative pole structure and by improve cathode invertibity.However, since this film formation reaction is irreversible
, so causing the consumption of lithium ion, reduce battery capacity.In addition, the first charge-discharge due to certain carbon based negative electrodes materials is imitated
Rate is lower, so as the increase of cycle-index causes the consumption of lithium ion, therefore electrode capacity declines, and leads to cycle life most
Decline eventually.
Therefore, the method for prelithiation carbon electrode is actively studied.Typically, consider by physical-chemical process will be electric
Method, method of electrochemistry prelithiation carbon electrode of electrode etc. are prepared after the active material lithiumation of pole, meanwhile, electrode active material
Pre- embedding lithium be improve lithium-ion capacitor performance an important method；Compare the energy and horse-power formula (E=of capacitor
CV2/ 2, P=V2/ 4R), it can be seen that voltage improves, and energy and power are substantially improved；And pre- embedding lithium can reduce electrode
Current potential, improves the voltage of lithium-ion capacitor, to improve the power and energy response of capacitor.
On the one hand, physical method is by transmitting lithium foil or lithium powder and cathode between upper roller and lower roll to carry out roller to it
It presses the method for cathode dipping lithium, has in this way because environmental factor is such as burnt as having due to implementation at high temperature
With the danger of explosion.
On the other hand, since electrochemical process is implemented at room temperature, so the danger such as burnt and exploded is lower than physico
Method.However, the process of electrochemical process is complicated and difficult.In addition, conventional prelithiation method has advantage, such as obvious low adds
Work speed, due to the roll-in together with cathode of lithium foil, lithium powder caused by lithium be difficult to remove and be difficult to recycle.
In addition, in conventional prelithiation method, due to only when lithium powder, lithium foil and cathode pass through between upper roller and lower roll or
Cathode is impregnated using lithium, it is difficult to control reacting dose and there are the probability of uncharged lithium height.
Therefore, the technology of this problem in the urgent need to address.In this regard, the invention discloses one kind to be used for lithium-ion electric
The preparation method of the prelithiation gel electrolyte of container adds lithium powder as prelithiation lithium source, electrolyte in gel electrolyte
Surface lithium powder directly and cathode contact can achieve the effect that the pre- embedding lithium of physics, in addition, the method is compared to the pre- embedding lithium of chemistry, work
Sequence is simple.After completing device assembling, carries out constant current charge-discharge and carry out the pre- embedding lithium of profound electrochemistry, film formation reaction is at this moment
Implement.It, can be not due to film formation reaction and during initial charge when using the carbon electrode of prelithiation as cathode
The lithium-ion capacitor of high capacity is manufactured in the case where the capacity decline shown, in addition, increasing lithium ion with cycle-index
Consumption is supplemented by lithium powder, so cycle life can be obviously prolonged.
Summary of the invention
The unsolved other technologies problem of Buddhist monk to solve the above-mentioned problems, one of the objects of the present invention is to provide one kind
For the prelithiation gel electrolyte of lithium-ion capacitor, the electrolyte meter reveals high ionic conductivity, and wide electrochemistry is steady
Determine window, good thermal stability and chemical stability, good filming performance, simple process is easy to process.
As it is a variety of careful and it is extensive research and experiment as a result, present inventors have developed the sides of prelithiation cathode
Method, wherein production efficiency can be improved by reducing process time, it is easy to accomplish large-scale production.
According to an aspect of the present invention, a kind of prelithiation gel electrolyte for lithium-ion capacitor is provided, it is described
Electrolyte is made of porous polymer copolymer fixation in situ ionic liquid electrolyte, lithium powder, and ionic liquid electrolyte is by room temperature
For the ionic liquid and lithium salts of liquid.
It is preferred that high molecular polymer are as follows: Kynoar (PVDF) Kynoar-hexafluoropropylene copolymer (PVDF-
hfp)；Polyethylene glycol oxide (PEO), one kind of polyvinyl chloride (PVC), polyacrylonitrile (PAN), polymethyl methacrylate (PMMA)
Or it is several.
It is preferred that the aperture of high molecular polymer porous network is nanoscale.
Preferred ion liquid are as follows: the double fluoroform sulfonamides of 1- ethyl-3-methylimidazole, 1- third class base -3- methylimidazole
The double fluoroform sulfonamides of double fluoroform sulfonamides, 1- butyl -3- methylimidazole, N- methyl, the double trifluoro methylsulphurs of propylpiperdine
Imide salts, N- methyl, butyl piperidine bis-trifluoromethylsulfoandimide salt, N- methyl, propyl pyrrole alkane bis-trifluoromethylsulfoandimide
Salt, N- methyl, the one or more of butyl pyrrolidine bis-trifluoromethylsulfoandimide salt etc..
Preferred ion liquid-liquid and the molal weight of high molecular polymer ratio are 1:10-10:1.
A kind of prelithiation gel electrolyte for lithium-ion capacitor belonging to according to claim 1, it is characterised in that:
Lithium salts are as follows: double trifluoromethanesulfonimide lithiums, LiCl, LiBr, LiI, LiClO, LiBF4、LiB10Cl10、LiPF6、LiCF3SO3、
LiCF3CO2、LiAsF6、LiSbF6、LiAlCl4、CH3SO3Li、CF3SO3Li、(CF3SO2)2NLi, chloroborane lithium, lower aliphatic carboxylic
The one or more of sour lithium and tetraphenylboronic acid lithium etc..
The content of lithium salts is 0.1-20wt% in preferred ion liquid electrolyte.
It is preferred that lithium powder are as follows: the one of passivation of lithium powder, Li-Si Alloy Powder, lithium-aluminium alloy powder, lithium boron alloy powder, lithium-zinc alloy powder etc.
Kind is several.
It is preferred that passivation of lithium powder content is 0.01-10wt%.
A kind of preparation method step of lithium ion battery of the present invention, lithium-ion capacitor prelithiation gel electrolyte
It is rapid as follows: (1), to disperse high-molecular copolymer in organic solvent in inert gas environment and obtain mixed system, heating is stirred
It mixes uniformly；By ionic liquid, lithium salts, passivation of lithium powder sequentially adds the mixed system, and solution, which pours vacuum drying polymerization and formed, to coagulate
Glue electrolyte.(2), prelithiation gel electrolyte obtained by step (1) and electrode material are assembled into lithium-ion capacitor.It carries out permanent
The processing of charge and discharge prelithiation is flowed, lithium ion battery, lithium ion super capacitor of prelithiation cathode etc. are obtained.
Preferable organic solvent includes: acetone, N-Methyl pyrrolidone, acetonitrile, benzene, toluene, dichloro-benzenes, methylene chloride, second
Ether, petroleum ether, n-hexane, cyclohexanone, toluene cyclohexanone pentane, ethylene glycol monoethyl ether etc. it is one or more.
The mass ratio of preferable organic solvent and high-molecular copolymer is 1:1-10:1.
It is preferred that the temperature range of agitating and heating is 20 DEG C -80 DEG C.
It is preferred that being 1-48h by gel electrolyte vacuum drying time range.
It is preferred that drying temperature range is 20-120 DEG C
The current density of constant current prelithiation is 0.01-10A/g, and cycle-index is 1-1000 times.
A kind of lithium-ion capacitor, it is characterised in that: the electrolyte that the device uses is a kind of for lithium-ion capacitance
The prelithiation gel electrolyte of device.
It is preferred that cathode may include carbon-based material and/or Si as negative electrode active material.
It is preferred that carbon-based material can be selected from least one of following substance substance: artificial crystalline graphite, native crystal
Graphite, amorphous hard carbon, low crystallization soft carbon, carbon black, acetylene black, Ketjen black, Super-P, graphene and fibrous carbon.
It is preferred that carbon-based material can be artificial crystalline graphite and/or native crystal graphite.
1. described the present invention provides a kind of prelithiation gel electrolyte of the present invention for lithium-ion capacitor
Electrolyte has excellent chemical property, the cohesiveness of solid and the dispersion conductibility of liquid: the electrolyte is containing rich
Rich nano pore structure has stronger ionic liquid adsorption capacity, big to ionic liquid electrolyte adsorption capacity, has height
Ionic conductivity, cycle life and reliability are good at room temperature；
2. the present invention provides a kind of prelithiation gel electrolyte of the present invention for lithium-ion capacitor, the electricity
Solving matter has good filming performance, and mechanical strength is easily processed into type；
Detailed description of the invention
Fig. 1 is scanning electron microscope (SEM) figure for the prelithiation gel electrolyte that embodiment 4 is prepared
Fig. 2 is that the prelithiation gel electrolyte that embodiment 4 is prepared is placed between two parallel stainless steel electrodes, in room
AC impedance spectral curve under temperature.
Fig. 3 is the ionic conductivity variation with temperature situation for the prelithiation gel electrolyte that embodiment 4 is prepared.
Fig. 4 is the prelithiation gel electrolyte and positive-active carbon resistance rod that embodiment 1 is prepared, cathode hard carbon electrode group
The cyclic voltammetry curve of the lithium ion gel supercapacitor of dress.
Fig. 5 is the prelithiation gel electrolyte and positive-active carbon resistance rod that embodiment 1 is prepared, cathode hard carbon electrode group
The constant current charge-discharge curve of the lithium ion gel supercapacitor of dress.
Fig. 6 is the prelithiation gel electrolyte and positive-active carbon resistance rod that embodiment 1 is prepared, cathode hard carbon electrode group
The lithium ion gel supercapacitor of dress is from the lithium ion gel supercapacitor to add passivation of lithium powder in different current densities
The correlation curve of lower specific capacity.
Fig. 7 is the prelithiation gel electrolyte and positive-active carbon resistance rod that embodiment 1 is prepared, cathode hard carbon electrode group
The energy density and function of the lithium ion gel supercapacitor of dress and the lithium ion gel supercapacitor for addition passivation of lithium powder
The correlation curve of rate density.
Fig. 8 is the prelithiation gel electrolyte and positive-active carbon resistance rod that embodiment 1 is prepared, cathode hard carbon electrode group
Pair of the lithium ion gel supercapacitor of dress and the lithium ion gel supercapacitor ac impedance spectroscopy for addition passivation of lithium powder
Compare curve.
Specific embodiment
The invention will be further elaborated combined with specific embodiments below, but the present invention is not limited to embodiments once.
It is as follows to the prelithiation gel electrolyte test for being used for lithium-ion capacitor made from embodiment once:
(1) scanning electron microscope test: scanning electron microscope (SEM) instrument model are as follows: SU8020, by the electrolysis
Matter removes ionic liquid with acetonitrile extraction, and sample is made after drying, is scanned testing electronic microscope.
(2) X-ray diffraction (XRD) is tested: using model are as follows: and Smartlab (9), test parameter use Cu/K alpha ray,Voltage is 40KV, and electric current 100Ma, scanning speed is that 8 °/min step-length is 0.02 °, scanning angle be 10 °-
90°。
Electrochemical AC impedance (EIS) test: pass through electrolysis shown in the measurement of electrochemical impedance spectroscopy test method at room temperature
Matter ionic conductivity, method particularly includes: stainless steel/prelithiation gel electrolyte/stainless is prepared into using two panels stainless steel electrode
The electrolyte is linked on electrochemical workstation or IM6E analysis instrument by steel blocking electrode, carries out testing impedance, test ginseng
Number；Alternating voltage amplitude 5mV, frequency range 1*10-2Hz-1*105Hz；According to the area of the thickness of electrolyte and stainless steel point solution
The conductivity of the electrolyte is calculated.
Embodiment 1
It weighs 0.5g Kynoar-hexafluoropropylene copolymer to mix with 3g N-Methyl pyrrolidone, stirring is until poly- inclined
Viton copolymers are completely dissolved, and weigh 0.5g 1- ethyl-3-methylimidazole tetrafluoroborate respectively, and 0.3g is bis-
Stirring in trifluoromethanesulfonimide lithium merging mixed system obtains clarification mixed system, adds into mixed system until dissolution
Enter 0.005g passivation of lithium powder, until after mixing evenly, pouring the mixture into stainless steel mould, is aged 6 hours, reaction generates solidifying
Glue, above procedure carry out in the glove box full of argon gas；Then gel is moved into 60 DEG C of baking ovens and is dried in vacuo 48h, obtained
To transparent lithium ion battery, lithium-ion capacitor prelithiation gel electrolyte.
(1) scanning electron microscope (SEM) is tested
The electrolyte known to SEM test has nanoporous network structure abundant, ionic liquid, lithium salts, passivation of lithium
Powder is limited wherein；
(2) electrochemical AC impedance (EIS) is tested
EIS test show the electrolyte 20 DEG C of internal resistances be 6.3 Ω, ionic conductivity 6.17*10-4Scm-1。
Embodiment 2
It weighs 0.5g Kynoar-hexafluoropropylene copolymer to mix with 3g acetone, stir until Kynoar-hexafluoro
Propylene copolymer is completely dissolved, and weighs 0.5g 1- ethyl-3-methylimidazole tetrafluoroborate, the bis- fluoroform sulphurs of 0.3g respectively
Imide li is placed in stirring in mixed system until dissolving, and obtains clarification mixed system, and it is blunt that 0.005g is added into mixed system
Change lithium powder, until after mixing evenly, pouring the mixture into stainless steel mould, is aged 6 hours, reaction generates gel, above procedure
Carried out in the glove box full of argon gas；Then will gel move into 60 DEG C of baking ovens in be dried in vacuo 48h, obtain transparent lithium from
Sub- battery, lithium-ion capacitor prelithiation gel electrolyte.
(1) scanning electron microscope (SEM) is tested
The electrolyte known to SEM test has nanoporous network structure abundant, ionic liquid, lithium salts, passivation of lithium
Powder is limited wherein；
(2) electrochemical AC impedance (EIS) is tested
EIS test show the electrolyte 20 DEG C of internal resistances be 5.2 Ω, ionic conductivity 8.13*10-4Scm-1。
Embodiment 3
It weighs 0.5g Kynoar-hexafluoropropylene copolymer to mix with 3g acetone, stir until Kynoar-hexafluoro
Propylene copolymer is completely dissolved, and weighs 0.5g 1- ethyl-3-methylimidazole tetrafluoroborate, the bis- fluoroform sulphurs of 0.3g respectively
Imide li is placed in stirring in mixed system until dissolving, and obtains clarification mixed system, and 0.01g passivation is added into mixed system
Lithium powder is aged 6 hours until after mixing evenly, pouring the mixture into stainless steel mould, and reaction generates gel, and above procedure is equal
It is carried out in the glove box full of argon gas；Then gel is moved into 60 DEG C of baking ovens and is dried in vacuo 48h, obtain transparent lithium ion
Battery, lithium-ion capacitor prelithiation gel electrolyte.
(1) scanning electron microscope (SEM) is tested
The electrolyte known to SEM test has nanoporous network structure abundant, ionic liquid, lithium salts, passivation of lithium
Powder is limited wherein；
(2) electrochemical AC impedance (EIS) is tested
EIS test show the electrolyte 20 DEG C of internal resistances be 3.4 Ω, ionic conductivity 1.22*10-3Scm-1。
It is as follows to the prelithiation gel electrolyte test for being used for lithium-ion capacitor made from embodiment once:
Electrochemical AC impedance (EIS) test: prelithiation lithium is measured by electrochemical impedance spectroscopy test method at room temperature
Ionic gel supercapacitor, method particularly includes: the lithium ion gel supercapacitor of the prelithiation cathode is linked to electricity
On chem workstation or IM6E analysis instrument, testing impedance, test parameter are carried out；Alternating voltage amplitude 5mV, frequency range 1*
10-2Hz-1*105Hz。
Cyclic voltammetric (CV) test: using model chi660e electrochemical workstation, and test parameter is to use at room temperature
0-4.2V voltage range sweeps speed respectively with different voltage: 10Mv/s, 20Mv/s, 30Mv/s, 50Mv/s, 70Mv/s and
100Mv/s carries out charge-discharge test.
Constant current charge-discharge test: using model chi660e electrochemical workstation, and test parameter is to use at room temperature
0-4.2V voltage range, respectively with different current densities: 0.5A/g, 1A/g, 2A/g, 4A/g, 6A/g, 8A/g, 10A/g, into
Row charge-discharge test.
Embodiment 4
Choose example 3 prepare prelithiation gel electrolyte, collocation active carbon anode, hard carbon cathode be assembled into button lithium from
Sub- gel supercapacitor.It activates within static 6 hours, then this device is carried out with the current density of 0.05A/g permanent at room temperature
Current charging and discharging prelithiation, 20 circle of circulation.It obtains the lithium ion gel supercapacitor of prelithiation cathode and tests its electrochemistry
Performance.
(1) cyclic voltammetric (CV) is tested
Cyclic voltammetric (CV) test shows that the voltage window of the lithium ion gel supercapacitor of the prelithiation cathode is 0-
4.2V.There are redox peaks in 3.2V and 2.2V.
(2) constant current charge-discharge is tested
Constant current charge-discharge test shows the lithium ion gel supercapacitor of the prelithiation cathode in different current densities:
0.5A/g, 1A/g, 2A/g, 4A/g, 6A/g, 8A/g, 10A/g carry out charge-discharge test.The specific capacity being calculated is respectively
46.17161F/g, 39.77929F/g, 33.56537F/g, 28.14941F/g, 25.39049F/g, 23.64425F/g and
22.63202F/g。
(3) electrochemical AC impedance (EIS) is tested
It is 5.6 Ω that EIS, which tests the lithium ion gel supercapacitor for showing the prelithiation cathode in 20 DEG C of internal resistances,.
Claims (17)
1. a kind of prelithiation gel electrolyte for lithium-ion capacitor, it is characterised in that: the electrolyte is by porous high score
Sub- polymer in situ fixed ion liquid electrolyte, lithium powder are constituted, and ionic liquid electrolyte is the ionic liquid of liquid by room temperature
It is formed with lithium salts.
2. a kind of prelithiation gel electrolyte for lithium-ion capacitor according to claim 1, it is characterised in that: high
Molecularly Imprinted Polymer are as follows: Kynoar (PVDF), Kynoar-hexafluoropropylene copolymer (PVDF-hfp), polyethylene glycol oxide
(PEO), one or more of polyvinyl chloride (PVC), polyacrylonitrile (PAN), polymethyl methacrylate (PMMA).
3. a kind of prelithiation gel electrolyte for lithium-ion capacitor according to claim 1, which is characterized in that institute
State ionic liquid are as follows: the double fluoroform sulfonamides of 1- ethyl-3-methylimidazole, the double trifluoro methylsulphurs of 1- third class base -3- methylimidazole
The double fluoroform sulfonamides of amidic-salt, 1- butyl -3- methylimidazole, N- methyl, propylpiperdine bis-trifluoromethylsulfoandimide salt, N-
Methyl, butyl piperidine bis-trifluoromethylsulfoandimide salt, N- methyl, propyl pyrrole alkane bis-trifluoromethylsulfoandimide salt, N- methyl, fourth
One or more of base pyrrolidines bis-trifluoromethylsulfoandimide salt.
4. a kind of prelithiation gel electrolyte for lithium-ion capacitor belonging to according to claim 1, it is characterised in that: lithium
Salt are as follows: double trifluoromethanesulfonimide lithiums, LiCl, LiBr, LiI, LiClO, LiBF4、LiB10Cl10、LiPF6、LiCF3SO3、
LiCF3CO2、LiAsF6、LiSbF6、LiAlCl4、CH3SO3Li、CF3SO3Li、(CF3SO2)2NLi, chloroborane lithium, lower aliphatic carboxylic
The one or more of sour lithium and tetraphenylboronic acid lithium etc..
5. a kind of prelithiation gel electrolyte for lithium-ion capacitor described in -4 according to claim 1, which is characterized in that
The molal weight of the ionic liquid and high-molecular copolymer ratio is 1:10-10:1；The content of lithium salts in ionic liquid electrolyte
For 0.1-20 wt%.
6. a kind of prelithiation gel electrolyte for lithium-ion capacitor belonging to according to claim 1, which is characterized in that institute
State lithium powder are as follows: one or more of passivation of lithium powder, Li-Si Alloy Powder, lithium-aluminium alloy powder, lithium boron alloy powder, lithium-zinc alloy powder.
7. a kind of prelithiation gel electrolyte for lithium-ion capacitor according to claim 1, it is characterised in that: lithium
Powder content is 0.01-10 wt%.
8. a kind of preparation method of prelithiation gel electrolyte for lithium-ion capacitor described in claim 1, feature
It is, includes the following steps: (1), disperses high-molecular copolymer in organic solvent in inert gas environment and mixed
System, heating stirring are uniform；By ionic liquid, lithium salts, lithium powder sequentially adds the mixed system, and solution is poured, is dried in vacuo, most
End form is at gel electrolyte；(2), prelithiation gel electrolyte obtained by step (1) and electrode material are assembled into lithium-ion electric
Container.The processing of constant current charge-discharge prelithiation is carried out, the lithium ion super capacitor etc. of prelithiation cathode is obtained.
9. a kind of preparation method of prelithiation gel electrolyte for lithium-ion capacitor according to claim 8,
It is characterized in that, the organic solvent includes: acetone, N-Methyl pyrrolidone, acetonitrile, benzene, toluene, dichloro-benzenes, methylene chloride, second
Ether, petroleum ether, one of n-hexane, cyclohexanone, toluene cyclohexanone pentane, ethylene glycol monoethyl ether or a variety of.
10. a kind of preparation method of prelithiation gel electrolyte for lithium-ion capacitor according to claim 8,
Be characterized in that: the mass ratio of organic solvent and high-molecular copolymer is 1:1-10:1.
11. a kind of preparation method of prelithiation gel electrolyte for lithium-ion capacitor according to claim 8,
Be characterized in that: the temperature range of agitating and heating is 20 DEG C -80 DEG C.
12. a kind of preparation method of prelithiation gel electrolyte for lithium-ion capacitor according to claim 8,
It is characterized in that: being 1-48h by gel electrolyte vacuum drying time range, temperature range is 20-120 DEG C.
13. a kind of preparation method of prelithiation gel electrolyte for lithium-ion capacitor according to claim 8,
Be characterized in that: the current density of constant current prelithiation is 0.01-10A/g, and cycle-index is 1-1000 times.
14. a kind of lithium-ion capacitor, it is characterised in that: the electrolyte that the device uses is as described in claim 1 one
Kind lithium ion super capacitor prelithiation gel electrolyte.
15. a kind of lithium-ion capacitor according to claim 14, cathode includes carbon-based material and/or Si as cathode
Active material.
16. a kind of lithium-ion capacitor according to claim 15, the carbon-based material be in following substance extremely
Few a kind of substance: artificial crystalline graphite, native crystal graphite, amorphous hard carbon, low crystallization soft carbon, carbon black, acetylene black, section's qin
Black, Super-P, graphene and fibrous carbon.
17. a kind of lithium-ion capacitor according to claim 15, the carbon-based material be artificial crystalline graphite and/or
Native crystal graphite.
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| CN111122018A (en) * | 2019-12-13 | 2020-05-08 | 天津大学 | Method for preparing dielectric layer based on anisotropic wet etching, dielectric layer and flexible pressure sensor |
| CN112201846A (en) * | 2020-10-15 | 2021-01-08 | 中国第一汽车股份有限公司 | Solid electrolyte membrane and preparation method and application thereof |
| CN113346046A (en) * | 2021-06-01 | 2021-09-03 | 清华大学 | Composite metal lithium cathode capable of reducing lithium salt consumption and preparation method thereof |
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