CN108565125A - Prelithiation lithium ion super capacitor cathode, preparation method and lithium ion super capacitor - Google Patents
Prelithiation lithium ion super capacitor cathode, preparation method and lithium ion super capacitor Download PDFInfo
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- CN108565125A CN108565125A CN201810266638.8A CN201810266638A CN108565125A CN 108565125 A CN108565125 A CN 108565125A CN 201810266638 A CN201810266638 A CN 201810266638A CN 108565125 A CN108565125 A CN 108565125A
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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
- 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
- H01G11/22—Electrodes
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
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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
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
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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
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/42—Powders or particles, e.g. composition thereof
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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
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/50—Electrodes characterised by their material specially adapted for lithium-ion capacitors, e.g. for lithium-doping or for intercalation
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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
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
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- 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
Disclose a kind of prelithiation super capacitor anode, preparation method and lithium ion super capacitor.Lithium ion super capacitor cathode includes by active material and the negative material that constitutes of lithium metal skeleton carbon composite without lithium, and the content of the lithium metal skeleton carbon composite is 2% the 20% of negative material gross mass by percentage to the quality.For lithium ion super capacitor device during shelving, the carbon recombination reaction in cathode in the lithium metal of lithium metal framework carbon material and active material without lithium forms lithium carbon compound, makes up the loss of the lithium ion in device work；Framework carbon material provides porous structure for cathode simultaneously, it is ensured that the infiltration of electrolyte improves the energy density of device.
Description
Technical field
The present invention relates to electrochemical energy storage technical fields, more particularly to lithium ion super capacitor cathode, preparation method
And lithium ion super capacitor.
Background technology
With the development of economy, a large amount of uses of traditional fossil fuel cause global warming and haze harsh weather increasingly tight
Weight, taps a new source of energy as the task of top priority.In recent years people carried out hybrid power, fuel cell, chemical cell product and
The research and development of application achieve certain effect.But it is short for their intrinsic service lifes, temperature characterisitic is poor, change
The deadly defects such as battery pollution environment, system complex, cost be high are learned, never good solution.Lithium ion super
Capacitor has the advantages such as power density is high, the charge and discharge time is short, have extended cycle life, operating temperature range is wide.Therefore, Ke Yiguang
It is general to be applied to the different application scenarios such as auxiliary peak power, stand-by power supply, storing, regenerating energy, substitute electric power, it is controlled in industry
The various fields such as system, electric power, communications and transportation, intelligence instrument, consumer electronic product, national defence, communication, new-energy automobile have huge
Big application value and market potential.
Traditional ultracapacitor is designed based on electric double layer principle, and the energy density of integral device is 5-
8wh/kg, lower energy density cause device higher in application end cost, cannot be satisfied need of the application end for energy density
It asks.Lithium ion super capacitor uses the electrolyte containing lithium ion, has widened the electrochemical window of device, while at work
Lithium ion and active material reaction provide a part of capacity, therefore lithium ion super capacitor has higher energy density, and
And also the high power density and long circulation life of holding capacitor device the advantages of.In order to obtain the lithium ion super of higher energy density
Capacitor, simultaneously as lithium ion super capacitor can consume lithium ion in charge and discharge process, reduce in electrolyte effectively from
The concentration of son needs to carry out prelithiation to electrode (cathode).
Lithium ion super capacitor prelithiation is mainly used lithium band or lithium powder through dry laminating in active electricity at present
The lithium item that thickness is 33 microns is compounded in active electrode surface by pole surface, such as General Capacitor companies of the U.S., it
Lithium ion super capacitor device is formed afterwards, and prelithiation (Journal of The are carried out by electrolyte and lithium metal reaction
Electrochemical Society,164(2)A93-A98(2017)).Also it has been reported that being compounded in cathode using lithium powder
Surface is assembled into device, carries out prelithiation (213 (2012) 180-185 of Journal of Power Sources).On but
The method stated either uses lithium item or lithium powder progress prelithiation, and process needs the long period, and there are prelithiation not
Fully, leading to electrode surface, there are lithium residuals, this will influence cyclical stability and the safety of integral device；In addition, this
Prelithiation method needs first to obtain pole piece, then carries out compound, increases processing step, reduces production efficiency.
Invention content
One of main object of the present invention is to provide a kind of prelithiation lithium ion super capacitor cathode, preparation method
And lithium ion super capacitor, with overcome the deficiencies in the prior art.
The present invention carries out prelithiation using lithium metal-skeleton carbon composite to cathode, widens device operating voltages, simultaneously
The loss for making up the lithium ion in device work maintains lithium concentration in electrolyte to be held essentially constant, super to improve
The energy density of capacitor.
Present invention employs following technical solutions：
A kind of lithium ion super capacitor cathode is provided in some embodiments, and the cathode includes by the activity without lithium
The negative material that material and lithium metal-skeleton carbon composite are constituted, the content of the lithium metal-skeleton carbon composite is with matter
Measure the 2%-20% that percentages are negative material gross mass.
A kind of method preparing above-mentioned lithium ion super capacitor cathode, the method packet are provided in some embodiments
It includes：
It will be containing whether there is or not the coatings of the negative material slurry of the active material of lithium and the mixture of lithium metal-skeleton carbon composite
In in metal collector, cathode pole piece is formed；Alternatively, by containing whether there is or not the negative material slurries of the active material of lithium to be coated on metal
On collector, is formed containing whether there is or not the coatings of the active material of lithium, lithium metal-skeleton carbon composite is then passed through into pressure mode
It evenly spreads in the coating.
A kind of lithium ion super capacitor is provided in some embodiments, and the lithium ion super capacitor includes above-mentioned negative
Pole.
The present invention at least one of can have the advantages that：
(1) lithium metal in lithium ion super capacitor cathode-skeleton carbon composite is micro/nano level particle composition, gold
Belong to lithium to be present in the hole of porous carbon materials carrier on surface, such lithium metal can be easily from lithium metal-skeleton
Carbon composite discharges, to supplement the consumption of lithium ion in electrolyte.
(2) the stephanoporate framework carbon material in lithium metal-skeleton carbon composite can also provide porous structure for cathode, really
The infiltration for protecting electrolyte, improves the energy density of device.
(3) preparation process is simple, can be mass.
Description of the drawings
Fig. 1 is in embodiment 1 by the lithium ion super capacitance (1) of addition lithium carbon material prelithiation and not by adding lithium
The correlation curve of the cycle and energy density of the lithium ion super capacitor (2) of carbon material prelithiation.
Fig. 2 be under 1C multiplying powers in embodiment 1 by adding the lithium ion super capacitance (1) of lithium carbon material prelithiation and not leading to
Cross the charging and discharging curve of the lithium ion super capacitor (2) of addition lithium carbon material prelithiation.
Fig. 3 be under 3C multiplying powers in embodiment 2 by adding the lithium ion super capacitance (1) of lithium carbon material prelithiation and not leading to
Cross the charging and discharging curve of the lithium ion super capacitor (2) of addition lithium carbon material prelithiation.
Fig. 4 be under 10C multiplying powers in embodiment 3 by add the lithium ion super capacitance (1) of lithium carbon material prelithiation with not
By the charging and discharging curve for adding the lithium ion super capacitor (2) of lithium carbon material prelithiation.
Specific implementation mode
One aspect of the present invention provides a kind of lithium ion super capacitor cathode, which includes by the activity without lithium
Include micro/nano level in the negative electrode material layer for the negative material or the cathode that material and lithium metal-framework carbon material are constituted
Lithium alloy-skeleton carbon composite and the active material without lithium.
In some embodiments, lithium ion super capacitor cathode includes collector, and cathode is formed on the collector
Material layer.Collector can be made of copper foil, nickel foil or other metal foils；Collector can also be by porous metal material structure
At, including foam metal, punch metal and metal mesh.In some embodiments, the thickness of metal foil can be in 6-20 microns of models
In enclosing, surface roughness can be Ra 0.2-0.38.In some embodiments, foam metal may include foam copper, foam
Nickel, foamed iron and foamed alloy, such as foam iron-nickel and foam cupro-nickel.The thickness of foam metal can be in 10-300um ranges
It is interior, porosity can within the scope of 30-85%, pore-size distribution can for 10~150PPI according to different foam metal materials and
It is different.
In the present invention, " active material for being free of lithium " or " active material of no lithium " refers to without active lithium (that is, cannot
Enough release lithium metal or lithium ion) negative material.In some embodiments, the active material of no lithium is conductive carbon material
Material.
In some embodiments, the active material of no lithium can be selected from least one of graphite, hard carbon, soft carbon.
In some embodiments, the content of lithium metal-skeleton carbon composite is that negative material is total by percentage to the quality
The 2%-20% of quality.
In some embodiments, in lithium ion super capacitor cathode lithium metal-skeleton carbon composite surface density (
Quality on collection liquid surface unit area) can be 1-10mg/cm2, preferably 3-5mg/cm2。
In some embodiments, lithium metal-skeleton carbon composite is the micro/nano level that grain size is 10 nanometers -100 microns
Particle or powder, it includes porous carbon materials carriers and the lithium metal being present in porous carbon materials carrier hole and surface.
In some embodiments, the content of lithium metal by percentage to the quality can be in lithium metal-skeleton carbon composite
For 10%-95%, such as 10-80%, 20-70%, 50%-60% etc..
In some embodiments, framework carbon material carrier may include carbon fiber microballoon, porous carbon nanotube microballoon and second
At least one of acetylene black.
In some embodiments, framework carbon material carrier is porous carbon nanotube microballoon, is mutually handed over by carbon nanotube
Twine reunion and formation, the microballoon with nanoscale hole on internal and surface, microspherulite diameter is 1-100 microns.It is such
Microballoon has approximate solid structure (similar ball of yarn structure), i.e., carbon nanotube or carbon nano-fiber are full of inside microballoon, but
Be entwine reunion carbon nanotube or carbon nano-fiber between there are nanoscale hole, these holes can be used for accommodate metal
Lithium particle.
In some embodiments, it can be 1 μm~100 μ that carbon nanotube microballoon, which is spherical or near-spherical particle, average diameter,
M, preferably 1 μm~25 μm；Specific surface area can be 100~1500m2/ g, preferably 150~500m2/g；Contained hole in microballoon
The pore-size distribution of gap can be 1~200nm, preferably 1~50nm.
In some embodiments, carbon nanotube microballoon at least have tiny spherical solid aggregated structure, spherical aggregated structure,
Any one in spherical aggregated structure, porous spherical aggregated structure and bread cast aggregated structure.
In some embodiments, carbon nanotube includes in multi-walled carbon nanotube, double-walled carbon nano-tube and single-walled carbon nanotube
Any one or two or more combinations, the carbon nanotube optionally passes through surface-functionalized processing.It modifies in carbon nanotube
The group on surface may be selected from but not limited to-COOH ,-OH ,-NH2Equal groups.
In some embodiments, carbon nanotube microballoon can form dispersion liquid by the way that carbon nanotube to be scattered in solvent,
Then it is spray-dried and prepares.For example, preparation method may comprise steps of：
A, carbon nanotube is distributed to by being ultrasonically treated in dispersion solvent (being free of surfactant), obtains dispersion liquid；
B, the dispersion liquid obtained in step A is sprayed by the nozzle of spray dryer, presetting inlet air temperature and outlet air
Temperature, it is stirring that solution is kept in spray process；
C, cooling obtains carbon nanotube microballoon.
In some embodiments, the solvent use can make carbon nano-tube/carbon nano fabric and nano carbon particle uniform
Dispersion organic and/or inorganic liquid, for example, water, ammonium hydroxide, hydrochloric acid solution, ethyl alcohol, acetone, isopropanol any one or it is more
The combination of kind.
In some embodiments, it is 1 that the solvent, which can be volume ratio,:10 ethyl alcohol and the mixture of water.
In some embodiments, the condition of spray drying may include：Inlet air temperature is 150~250 DEG C, and leaving air temp is
75 DEG C or more, such as 75~150 DEG C, or be 90 DEG C or more；One preferred spray drying condition includes：Inlet air temperature is 190
~210 DEG C, leaving air temp is 90~110 DEG C.
In some embodiments, spray velocity when spray drying can be 1 ml/min to 100 liters/min.
In some embodiments, framework carbon material carrier is carbon fiber microballoon, the pattern and structure of the carbon fiber microballoon
It is similar with carbon nanotube microballoon, and can be prepared by similar spray drying process.
In some embodiments, framework carbon material carrier is acetylene black, and acetylene black used is purified acetylene gas in height
The lower isolation air of temperature carries out obtained by thermal cracking, and grain size is 20~100nm, preferred value 70-80nm；Specific surface be 120~
200m2/ g, preferred value are 140~160m2/g。
In some embodiments, lithium metal-skeleton carbon composite can be by by molten metal lithium and framework carbon material
Mixing obtains after cooling.The mixing may include by lithium metal and framework carbon material (for example, about 200 DEG C) stirring under heating
Mixing immerses framework carbon material in molten metal lithium.The preparation of lithium metal-skeleton carbon composite is in an inert atmosphere
It carries out, such as (the water content in the glove box of argon gas atmosphere<10ppm, oxygen content<10ppm).
In some embodiments, lithium metal-skeleton carbon composite is also passing through screening step before.For example, in argon
50-100 the polished standard screens are crossed in the glove box of gas shielded, collect lithium metal-skeleton carbon composite by sieve pore.
In some embodiments, lithium alloy-skeleton carbon composite can be prepared by the following method：
(1) by heating lithium metal to 180-220 DEG C of temperature, to obtain molten lithium；
(2) under the stirring of 500-800 revolutions per seconds of rotating speed, the molten lithium obtained in step (1) is warming up to 220~
1000℃
(3) what is obtained into the step (2) under the stirring in 500-800 revolutions per seconds of rotating speed is described in molten
Porous carbon materials carrier is added in the lithium alloy of state, continues stirring 20-40 minutes, to obtain lithium alloy-skeleton carbon composite.
Another aspect of the present invention provides a kind of method preparing above-mentioned lithium ion super capacitor cathode, including：It will
Containing whether there is or not the negative material slurries of the active material of lithium and the mixture of lithium metal-skeleton carbon composite to be coated on metal afflux
On body, cathode pole piece is formed；Also can by containing whether there is or not the negative material slurry of the active material of lithium be coated on metal collector on, shape
At containing whether there is or not the coatings of the active material of lithium, then lithium metal-skeleton carbon composite is evenly spread to by pressure mode
In the coating.
About " collector " and " lithium metal-skeleton carbon composite ", referring to the associated description of preceding sections.
In some embodiments, it is formed using coating method multiple containing the no lithium active material and lithium metal-skeleton carbon
The electrode material layer of composite blend comprising：
It (1) will be containing whether there is or not the active material of lithium, the lithium metal-electrode material layer of skeleton carbon composite mixture, bondings
Agent and optional conductive agent are dispersed in anhydrous solvent, and (herein, " anhydrous " refers to water content<In 50ppm), is formed and contain the nothing
The slurry that the electrode material layer of lithium active cathode material, lithium metal-skeleton carbon composite mixture is uniformly distributed therein；
(2) slurry obtained in step (1) is coated on collection liquid surface, is then dried to be formed containing the no lithium
The coating of active cathode material, lithium metal-skeleton carbon composite mixture.
Step (1) and (2) carry out in an inert atmosphere, for example, in the glove box (water content of argon gas protection<
10ppm, oxygen content<It is carried out in 10ppm) or in drying room (dew point is less than -40 DEG C).
Another aspect of the present invention provides a kind of lithium ion super capacitor, and the lithium ion super capacitor includes upper
The cathode stated.
In some embodiments, the anode of lithium ion super capacitor includes collector and is attached to the more of collection liquid surface
Hole carbon material, porous carbon materials can be at least one in carbon fiber, carbon nanotube, acetylene black, Ketjen black, graphene and activated carbon
Kind.
Following detailed description is intended to illustratively and in non-limiting manner illustrate the disclosure.
Specific implementation mode 1 is a kind of lithium ion super capacitor cathode, and the cathode includes the active material by no lithium
The negative material constituted with lithium metal-skeleton carbon composite, the content of the lithium metal-skeleton carbon composite is with quality hundred
Divide the 2%-20% than being calculated as negative material gross mass.
Specific implementation mode 2 is the lithium ion super capacitor cathode according to above-mentioned specific implementation mode 1, wherein institute
It includes collector and the electrode material layer that is attached on collection liquid surface to state cathode, and the electrode material layer includes the work by no lithium
Property the negative material that constitutes of material and lithium metal-skeleton carbon composite.
Specific implementation mode 3 is the lithium ion super capacitor cathode according to above-mentioned specific implementation mode 2, wherein institute
Collector is stated to be made of porous metal material or metal foil.
Specific implementation mode 4 is that the lithium ion super capacitor according to any one of above-mentioned specific implementation mode is negative
Pole, wherein the porous metal material includes foam metal, punch metal and metal mesh；And/or the metal foil includes copper foil
And nickel foil.
Specific implementation mode 5 is that the lithium ion super capacitor according to any one of above-mentioned specific implementation mode is negative
Pole, wherein quality of the lithium metal-skeleton carbon composite on the collection liquid surface unit area is 1-10mg/cm2,
It is preferred that 3-5mg/cm2。
Specific implementation mode 6 is that the lithium ion super capacitor according to any one of above-mentioned specific implementation mode is negative
Pole, wherein the lithium metal-skeleton carbon composite is micro/nano level of the average grain diameter in 10 nanometer of -100 micron range
Grain or powder, including porous carbon materials carrier and the lithium metal being present in the porous carbon materials carrier hole and surface.
Specific implementation mode 7 is the ion super capacitor anode according to any one of above-mentioned specific implementation mode,
The content of lithium metal is 10%-95% by percentage to the quality in wherein described lithium metal-skeleton carbon composite.
Specific implementation mode 8 is the lithium ion super capacitor according to any one of above-mentioned specific implementation mode 1-7
Cathode, wherein the porous carbon materials include at least one of carbon fiber microballoon, porous carbon nanotube microballoon and acetylene black.
Specific implementation mode 9 is that the lithium ion super capacitor according to any one of above-mentioned specific implementation mode is negative
Pole, wherein the porous carbon nanotube microballoon is mutually to be entwined reunite and formed, on internal and surface had by carbon nanotube
The microballoon of nanoscale hole, microspherulite diameter are 1-100 microns.
Specific implementation mode 10 is that the lithium ion super capacitor according to any one of above-mentioned specific implementation mode is negative
Pole, wherein the specific surface area of the carbon nanotube microballoon is 100~1500m2/g；
And/or the aperture of hole contained by the carbon nanotube microballoon is 1~200nm；
And/or the carbon nanotube microballoon at least has tiny spherical solid aggregated structure, spherical aggregated structure, class ball
Any one in shape aggregated structure, porous spherical aggregated structure and bread cast aggregated structure；
And/or the carbon nanotube includes arbitrary in multi-walled carbon nanotube, double-walled carbon nano-tube and single-walled carbon nanotube
A combination of one or more, the carbon nanotube optionally pass through surface-functionalized processing.
Specific implementation mode 11 is a kind of lithium preparing the prelithiation according to any one of specific implementation mode 1-10
The method of ion super capacitor anode, wherein the method includes：It will be containing whether there is or not the active materials of lithium and lithium metal-skeleton carbon
The negative material slurry of the mixture of composite material is coated in metal collector, forms cathode pole piece；Or it will contain that whether there is or not lithiums
The negative material slurry of active material be coated in metal collector, formed containing whether there is or not the coatings of the active material of lithium, then
Lithium metal-skeleton carbon composite is evenly spread to by pressure mode in the coating.
Specific implementation mode 12 is the method according to specific implementation mode 11, wherein the negative material slurry also wraps
Containing at least one of binder, dispersant and solvent.
Specific implementation mode 13 is a kind of lithium ion super capacitor, wherein the lithium ion super capacitor includes basis
Cathode described in any one of specific implementation mode 1-10.
Specific implementation mode 14 is the lithium ion super capacitor according to specific implementation mode 13, the lithium ion
Supercapacitor positive electrode includes collector and is attached to the active carbon material composition of collection liquid surface.
Specific implementation mode 15 is the lithium ion super capacitor according to specific implementation mode 14, wherein the skeleton
Carbon material includes carbon fiber microballoon, porous carbon nanotube microballoon and the one such or several combination of acetylene black.
In order to make the purpose , technical scheme and advantage of the present invention be clearer, with reference to the accompanying drawings and embodiments, right
The present invention is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, and
It is not used in the restriction present invention.As long as in addition, technical characteristic involved in the various embodiments of the present invention described below
It does not constitute a conflict with each other and can be combined with each other.
Postscript, used various products structural parameters, various reaction partners and technique item among following examples
Part is more typical example, but is verified by inventor's a large number of experiments, in the other different structures of those listed above
Parameter, other types of reaction partner and other process conditions are also applicable, and also equal attainable cost invention is claimed
Technique effect.
Synthetic example 1
200 ml deionized waters and 20 milliliters of ethyl alcohol are added in 2g multi-walled carbon nanotubes (Shandong great Zhan nanometers of Co., Ltd)
In, 130W ultrasonic probes are handled 5 hours so that carbon nanotube is uniformly dispersed in a solvent.Later, sample is added and is spray-dried
In machine (the refined journey experimental instruments and equipment limited in Shanghai, model YC-015), setup parameter is：Inlet air temperature is 200 DEG C, leaving air temp
It it is 150 DEG C, atomisation pressure 40MPa, sample size 500mL/h, spray drying gained is carbon nanotube microballoon.
In the glove box full of argon gas (moisture and oxygen content are not higher than 3ppm), by 10 grams of Battery grade lithium metals
(Tianjin China Energy Lithium Co., Ltd.) and 5 grams of carbon nanotube microballoons are added in the heater with stainless steel cauldron, are heated to
It 200 degrees Celsius, stirs 1 minute, 100 revs/min of mixing speed, is then heated to 230 DEG C, stir 20 minutes, stir data 500
Rev/min, it is cooled to room temperature, products obtained therefrom is lithium metal-skeleton carbon composite.
Synthetic example 2
The preparation of anode：According to Kynoar：Acetylene black：Active carbon material：Water=30mg：30mg：1000mg：15ml
Each substance is weighed, is placed in vial and is stirred overnight and (is more than 10 hours).Wherein Kynoar (Sigma-Aldrich) is viscous
Agent is tied, acetylene black is conductive agent, and activated carbon (Kuraray), water is solvent.The slurry stirred evenly is coated on nickel foil,
Blade thickness is 250 microns, and nickel foil thickness is 10 microns.60 DEG C of vacuum (- 0.1Mpa) dry pole piece overnight, then by drying
Pole piece cuts according to 56mm*43mm sizes and is molded, the anode pole piece as lithium ion super capacitance.
Embodiment 1
According to butadiene-styrene rubber：Polystyrene：Acetylene black：Lithium metal-skeleton carbon composite (is obtained by synthetic example 1
)：Hard carbon：Paraxylene=20mg：20mg：40mg：120mg：1000mg：10ml weighs each substance, is placed in vial and stirs
It mixes and (is more than 10 hours) overnight.Wherein butadiene-styrene rubber (Sigma-Aldrich) and polystyrene (Sigma-Aldrich) are to bond
Agent, acetylene black are conductive agent, hard charcoal (Shenzhen Bei Terui), and paraxylene (Shanghai Aladdin biochemical technology limited liability company) is
Solvent.The slurry stirred evenly is coated on copper foil, blade thickness is 250 microns, and copper thickness is 10 microns.60 DEG C of vacuum
(- 0.1Mpa) dries pole piece overnight, then cuts the pole piece of drying according to 58mm*45mm sizes and is molded, super as lithium ion
The cathode pole piece of grade capacitance.The above process (moisture≤3ppm, oxygen≤3ppm) in the glove box full of argon gas carries out.
Above-mentioned positive electrode pole piece, diaphragm, negative electrode pole piece are sequentially overlapped together, using aluminium foil as external package casing,
It is packaged after electrolyte is added, you can obtain the lithium ion super capacitance monomer of prelithiation.Wherein electrolyte is 1mol/L
LiPF6EC/DMC/DEC (vol 1/1/1, Dongguan Shan Shan battery materials Co., Ltd), diaphragm are that (it is new that Shenzhen is preced with power to PP diaphragms
Materials Co., Ltd Celgard 3105).The lithium ion super capacitor that prelithiation is made is carried out using Soft Roll test equipment
Charge and discharge cycles are tested.
Comparative example 1
According to butadiene-styrene rubber：Polystyrene：Acetylene black：Hard carbon：Paraxylene=20mg：20mg：40mg：1000mg：
10ml weighs each substance, is placed in vial and is stirred overnight and (is more than 10 hours).Wherein butadiene-styrene rubber (Sigma-Aldrich) and
Polystyrene (Sigma-Aldrich) is binder, and acetylene black is conductive agent, hard charcoal (Shenzhen Bei Terui), paraxylene (Shanghai
Aladdin biochemical technology limited liability company) it is solvent.The slurry stirred evenly is coated on copper foil, blade thickness 250
Micron, copper thickness are 10 microns.60 DEG C of vacuum (- 0.1Mpa) dry pole piece overnight, then by the pole piece of drying according to 58mm*
45mm sizes cut molding, the cathode pole piece as lithium ion super capacitance.The above process (water in the glove box full of argon gas
Divide content≤10ppm, oxygen≤10ppm) it carries out.
Above-mentioned positive electrode pole piece, diaphragm, negative electrode pole piece are sequentially overlapped together, using aluminium foil as external package casing,
It is packaged after electrolyte is added, you can obtain the lithium ion super capacitance monomer of non-prelithiation.Wherein electrolyte is 1mol/L
LiPF6EC/DMC/DEC (vol 1/1/1, Dongguan Shan Shan battery materials Co., Ltd, similarly hereinafter), diaphragm is PP diaphragms (Shenzhen
Guan Li new materials Co., Ltd Celgard 3105).Under the same test conditions to the ultracapacitor of non-prelithiation lithium ion
Carry out charge and discharge cycles test.
Fig. 1 is that the lithium ion super capacitance (curve 1) of prelithiation and the lithium ion super capacitance (curve 2) of non-prelithiation follow
The correlation curve of ring and energy density can be seen that the lithium ion super capacitor energy Jing Guo prelithiation from cycle performance curve
Metric density is higher than the lithium ion super capacitor of non-prelithiation.
Fig. 2 is the lithium ion of lithium ion super capacitance (curve 1) and non-prelithiation of prelithiation in embodiment 1 under 1C multiplying powers
Super capacitor (curve 2) charging and discharging curve, as can be seen from the figure the lithium ion super capacitor capacity of prelithiation is pre- higher than not
The lithium ion super capacitor of lithiumation.
Embodiment 2
According to butadiene-styrene rubber：Polystyrene：Acetylene black：Lithium metal-skeleton carbon composite (is obtained by synthetic example 1
)：Graphite：Paraxylene=15mg：20mg：50mg：100mg：750mg：23ml weighs each substance, is placed in vial and stirs
(it is more than 10 hours) overnight.Wherein butadiene-styrene rubber (Sigma-Aldrich) and polystyrene (Sigma-Aldrich) are to bond
Agent, acetylene black are conductive agent, graphite (Shenzhen Bei Terui), and paraxylene (Shanghai Aladdin biochemical technology limited liability company) is
Solvent.The slurry stirred evenly is coated on copper foil, blade thickness is 250 microns, and copper thickness is 10 microns.60 DEG C of vacuum
(- 0.1Mpa) dries pole piece overnight, then cuts the pole piece of drying according to 58mm*45mm sizes and is molded, super as lithium ion
The cathode pole piece of grade capacitance.The above process (moisture≤3ppm, oxygen≤3ppm) in the glove box full of argon gas carries out.
Above-mentioned positive electrode pole piece, diaphragm, negative electrode pole piece are sequentially overlapped together, using aluminium foil as external package casing, are added
It is packaged after entering electrolyte, you can obtain the lithium ion super capacitance monomer of prelithiation.Wherein electrolyte is 1mol/L
LiPF6EC/DMC/DEC (vol 1/1/1, Dongguan Shan Shan battery materials Co., Ltd), diaphragm are that (it is new that Shenzhen is preced with power to PP diaphragms
Materials Co., Ltd Celgard 3105).The lithium ion super capacitor that prelithiation is made is carried out using Soft Roll test equipment
Charge and discharge cycles are tested.
Fig. 3 is the lithium ion of lithium ion super capacitance (curve 1) and non-prelithiation of prelithiation in embodiment 2 under 3C multiplying powers
Super capacitor (curve 2) charging and discharging curve, as can be seen from the figure the lithium ion super capacitor capacity of prelithiation is pre- higher than not
The lithium ion super capacitor of lithiumation.
Embodiment 3
According to butadiene-styrene rubber：Polystyrene：Acetylene black：Lithium metal-skeleton carbon composite (is obtained by synthetic example 1
)：Soft carbon：Paraxylene=20mg：30mg：75mg：150mg：800mg：16ml weighs each substance, is placed in vial and stirs
(it is more than 10 hours) overnight.Wherein butadiene-styrene rubber (Sigma-Aldrich) and polystyrene (Sigma-Aldrich) are to bond
Agent, acetylene black are conductive agent, soft charcoal (Shenzhen Bei Terui), and paraxylene (Shanghai Aladdin biochemical technology limited liability company) is
Solvent.The slurry stirred evenly is coated on copper foil, blade thickness is 250 microns, and copper thickness is 10 microns.60 DEG C of vacuum
(- 0.1Mpa) dries pole piece overnight, then cuts the pole piece of drying according to 58mm*45mm sizes and is molded, super as lithium ion
The cathode pole piece of grade capacitance.The above process (moisture≤3ppm, oxygen≤3ppm) in the glove box full of argon gas carries out.
Above-mentioned positive electrode pole piece, diaphragm, negative electrode pole piece are sequentially overlapped together, using aluminium foil as external package casing, are added
It is packaged after entering electrolyte, you can obtain the lithium ion super capacitance monomer of prelithiation.Wherein electrolyte is 1mol/L
LiPF6EC/DMC/DEC (vol 1/1/1, Dongguan Shan Shan battery materials Co., Ltd), diaphragm are that (it is new that Shenzhen is preced with power to PP diaphragms
Materials Co., Ltd Celgard 3105).The lithium ion super capacitor that prelithiation is made is carried out using Soft Roll test equipment
Charge and discharge cycles are tested.
Fig. 4 be the lithium ion super capacitance (curve 1) of prelithiation and non-prelithiation in embodiment 3 under 10C multiplying powers lithium from
Sub- super capacitor (curve 2) charging and discharging curve, as can be seen from the figure the lithium ion super capacitor capacity of prelithiation is not higher than
The lithium ion super capacitor of prelithiation.
Embodiment 4
Lithium metal-skeleton carbon composite preparation process is as described in synthesis example 1.
Positive plate is prepared as described in synthesis example 2.
According to butadiene-styrene rubber：Polystyrene：Acetylene black：Hard carbon：Paraxylene=15mg：25mg：50mg：800mg：10ml
Each substance is weighed, is placed in vial and is stirred overnight and (is more than 10 hours).Wherein butadiene-styrene rubber (Sigma-Aldrich) and polyphenyl
Ethylene (Sigma-Aldrich) is binder, and acetylene black is conductive agent, hard charcoal (Shenzhen Bei Terui), paraxylene (Shanghai I
Fourth biochemical technology limited liability company) it is solvent.The slurry stirred evenly is coated on copper foil, blade thickness is 250 microns,
Copper thickness is 10 microns.60 DEG C of vacuum (- 0.1Mpa) dry pole piece overnight, then by the pole piece of drying according to 58mm*45mm
Size cuts molding.
About 100 milligrams of lithium metal-skeleton carbon composites are dispersed on above-mentioned electrode plates, applies pressure and makes metal
Lithium-skeleton carbon composite is firmly pressed in get compound cell negative electrode material on electrode plates, and the above process is full of argon
(moisture≤10ppm, oxygen≤10ppm) carries out in the glove box of gas..
Above-mentioned positive electrode pole piece, diaphragm, negative electrode pole piece are sequentially overlapped together, using aluminium foil as external package casing, are added
It is packaged after entering electrolyte, you can obtain the lithium ion super capacitance monomer of prelithiation.Wherein electrolyte is 1mol/L
LiPF6 EC/DMC/DEC (vol 1/1/1, Dongguan Shan Shan battery materials Co., Ltd), diaphragm are that PP diaphragms (are preced with power in Shenzhen
New material Co., Ltd Celgard 3105).Using Soft Roll test equipment to be made prelithiation lithium ion super capacitor into
Row charge and discharge cycles are tested.Charge-discharge performance is similar to Example 1 after tested.
It should be appreciated that the foregoing is merely illustrative of the preferred embodiments of the present invention, it is not intended to limit the invention, it is all at this
All any modification, equivalent and improvement etc., should be included in the protection model of the present invention made by within the spirit and principle of invention
Within enclosing.
Claims (9)
1. a kind of lithium ion super capacitor cathode of prelithiation, it is characterised in that the cathode includes the active material by no lithium
The negative material that material and lithium metal-skeleton carbon composite are constituted, the content of the lithium metal-skeleton carbon composite is with quality
Percentages are the 2%-20% of negative material gross mass.
2. the lithium ion super capacitor cathode of prelithiation according to claim 1, it is characterised in that the work of the no lithium
Property material be conductive carbon material.
3. the lithium ion super capacitor cathode of prelithiation according to claim 2, it is characterised in that the work of the no lithium
Property material be selected from graphite, hard carbon, at least one of soft carbon.
4. the lithium ion super capacitor cathode of prelithiation according to claim 1, it is characterised in that the lithium metal-bone
Frame carbon composite is micro/nano level particle or powder of the average grain diameter in 10 nanometer of -100 micron range, including porous carbon
Material carrier and the lithium metal being present in the porous carbon materials carrier hole and surface.
5. the lithium ion super capacitor cathode of prelithiation according to claim 4, it is characterised in that the skeleton carbon materials
Material includes carbon fiber microballoon, porous carbon nanotube microballoon and one kind in acetylene black or several combinations.
6. lithium ion super capacitor cathode according to claim 1, it is characterised in that the lithium metal-skeleton carbon is compound
The content of lithium metal is 10%-95% by percentage to the quality in material.
7. a kind of method for the lithium ion super capacitor cathode preparing the prelithiation described in any one of claim 1-6,
Be characterized in that the method includes：
It will be containing whether there is or not the negative material slurries of the active material of lithium and the mixture of lithium metal-skeleton carbon composite to be coated on gold
Belong on collector, forms cathode pole piece；Or
By containing whether there is or not the negative material slurries of the active material of lithium to be coated in metal collector, formed containing whether there is or not the active materials of lithium
Then the coating of material is evenly spread to lithium metal-skeleton carbon composite in the coating by pressure mode.
8. according to the method described in claim 7, it is characterized in that the negative material slurry also include binder, dispersant and
At least one of solvent.
9. a kind of lithium ion super capacitor, it is characterised in that the lithium ion super capacitor includes to appoint in claim 1-6
The lithium ion super capacitor cathode of prelithiation described in one.
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| WO2021195835A1 (en) * | 2020-03-30 | 2021-10-07 | 中能中科（天津）新能源科技有限公司 | Pre-lithiated negative electrode and preparation method therefor, and lithium ion battery and supercapacitor having pre-lithiated negative electrode |
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Application publication date: 20180921 |