CN105869917A - Method and spraying device for lithium pre-insertion for negative pole of lithium-ion capacitor - Google Patents
Method and spraying device for lithium pre-insertion for negative pole of lithium-ion capacitor Download PDFInfo
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- CN105869917A CN105869917A CN201610337473.XA CN201610337473A CN105869917A CN 105869917 A CN105869917 A CN 105869917A CN 201610337473 A CN201610337473 A CN 201610337473A CN 105869917 A CN105869917 A CN 105869917A
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- lithium
- ion capacitor
- pole piece
- embedding
- negative pole
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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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- 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 method for lithium pre-insertion for a negative pole of a lithium-ion capacitor. The method comprises steps as follows: a negative pole piece comprising lithium-insertable active substance layer and a current collector layer is prepared firstly, then metal lithium powder with the particle size distribution D99 not larger than 300 mu m and a lithium salt non-protonic organic solution of 0.1-1 M are evenly mixed in an atmosphere environment with the moisture content lower than 2 permillage, mixed slurry is prepared, then the negative pole piece in S10 is dried, the mixed slurry in S20 is evenly sprayed to the negative pole piece at least once in the atmosphere environment with the moisture content lower than 2 permillage, the negative pole piece is left to stand for 10 min-24 h after spraying each time, and finally, the negative pole piece which is subjected to spraying and left to stand in S30 is subjected to vacuum drying or dried under protection of nitrogen or argon. The invention further discloses a spraying device for lithium pre-insertion for the negative pole of the lithium-ion capacitor. The lithium insertion speed is controlled by controlling the spraying speed of the mixed slurry, the content of the lithium powder in a mixed turbid liquid and the concentration of an electrolyte, so that the safety of the lithium insertion technology is improved.
Description
Technical field
The invention belongs to lithium-ion capacitor technical field, be specifically related to the pre-of a kind of novel lithium-ion capacitor negative pole
Embedding lithium method, and its spray equipment.
Background technology
Lithium-ion capacitor (Li-ion Capacitor) is a kind of mechanism of new electrochemical power sources, combines electric double layer super capacitor
Device and the energy storage mechnism of lithium ion battery, by capacitor type active material (high-ratio surface Carbon Materials), lithium ion battery active material
(lithium intercalation active material) and organic lithium salt electrolyte are constituted.Lithium-ion capacitor has ultracapacitor and lithium ion battery concurrently
Electrochemical properties, can not only obtain excellent power and the life characteristic surmounting lithium ion battery, also possesses simultaneously and is better than double electricity
The energy density of layer ultracapacitor.Additionally, lithium-ion capacitor is also equipped with, self-discharge rate is low, operating voltage is high, operating temperature
The many advantages such as wide ranges and high security, at traffic power, engine start and stop, intelligent grid, uninterrupted power source and wind-force
The numerous areas such as generating have wide application prospect.
Comparing double layer capacitor, the reason that lithium-ion capacitor energy density promotes is, first, use specific capacity and
The higher embedding lithium type lithium ion battery material of compacted density；Second, make full use of electrode material current potential and electrolyte electrochemical window
The cooperation of mouth, promotes the operating voltage of capacitor.For the collocation mode of positive and negative pole material, the structure side of lithium-ion capacitor
Formula is broadly divided into two categories below: the first kind is using high-specific surface area Carbon Materials as negative pole, using high potential embedding lithium shaped material as
Positive pole；Equations of The Second Kind is then contrary, i.e. using high-specific surface area Carbon Materials as positive pole, using electronegative potential embedding lithium type pond material as negative pole.
Generally, the operating voltage of first kind lithium-ion capacitor is on the low side, generally at below 3V, be unfavorable for fully promoting lithium from
The energy density of sub-capacitor.Equations of The Second Kind lithium-ion capacitor, does positive pole with high-specific surface area Carbon Materials, coordinates the embedding lithium of electronegative potential
Type lithium ion battery material, as negative pole, can fully promote the operating voltage of lithium-ion capacitor, promote its energy density.When
When such lithium-ion capacitor does negative pole with Carbon Materials, owing to intercalation potential is low, thus its operating voltage can be promoted to 4.5V, from
And obtain higher specific energy, thus such lithium-ion capacitor more commercialization prospect, also become hot research direction.
The negative material of above-mentioned Equations of The Second Kind lithium-ion capacitor specifically includes that native graphite, Delanium, mesocarbon are micro-
Ball, coke, hard charcoal, CNT, Graphene etc. can embedding lithium material with carbon element or tin oxide, lithium titanate, titanium dioxide etc. can embedding lithium gold
Belong to the conducting polymer materials etc. such as oxide material or coalescence benzene.For promoting the operating voltage of lithium-ion capacitor, negative pole need to be made
Work under low current potential, so that above-mentioned material is carried out the most embedding lithium thus reduces its operating potential.Additionally, pre-embedding lithium
The application of technology can also reduce the irreversible capacity of negative material, thus promote lithium-ion capacitor further and compare energy.Not only
So, pre-embedding lithium technology can also promote the lithium concentration in lithium-ion capacitor electrolyte system, and lifter high rate performance is also
Extend cycle life.It may be said that pre-embedding lithium technology is key technology prepared by lithium-ion capacitor, be also restriction high specific energy lithium from
The Pinch technology of sub-capacitor industrialization.
The pre-embedding lithium technology of negative pole of lithium-ion capacitor is many realizes pre-embedding lithium using lithium metal as lithium source.At present, practical
The pre-embedding lithium method of lithium-ion capacitor negative pole be technology disclosed in Fuji Heavy Industries Zhu Shi club.I.e. in lithium-ion capacitor
Introducing lithium metal is as lithium source, and makes Lithium-ion embeding negative active core-shell material by the method for electrochemical contact, it is achieved that in situ
Pre-embedding lithium.For ensureing that in pre-process of intercalation, the movement of lithium ion is not hindered by electrode, this technology uses the metal forming with through hole
As both positive and negative polarity collector, ensure lithium ion walking between positive and negative electrode, it is achieved that the pre-embedding lithium of anticathode active material.
The pre-embedding lithium technology that Fuji Heavy Industries strain formula can be developed, is applied to field of lithium ion battery (Publication No. in early days
WO98/33227, the International Publication date is on July 30th, 1998, publication entitled Organic Electrolytic
Battery), its object is to, by pre-embedding lithium mode, reduce the irreversible capacity of agraphitic carbon negative pole.Along with lithium-ion capacitance
Device technology develops, this technology again by the creative lithium-ion capacitor field that is applied to (Publication No. US2004/0179328A1,
Publication date is on September 16th, 2014, publication entitled Organic Electrolyte Capacitor).Further
Ground, Fuji Heavy Industries strain formula can be in Publication No. CN101138058A, and publication date is on March 5th, 2008, publication title
In publication for " lithium-ion capacitor ", use the lithium-ion capacitor structure that lithium metal is set between both positive and negative polarity lamination unit
Above-mentioned pre-embedding lithium technology is improved by one-tenth mode, further increases the pre-embedding lithium efficiency of lithium-ion capacitor.
The pre-embedding lithium technology that above-mentioned Fuji Heavy Industries strain formula can be developed, by lithium metal preset in lithium-ion capacitor,
Achieve the pre-embedding lithium of original position of anticathode, there is stronger practicality.But, this technology still suffers from some problems to be solved.First
First, this technology uses the internal spontaneous embedding lithium of electrochemical contact mode, owing to lithium ion is more likely to embed close to lithium metal negative
Pole active material and with negative current collector through hole corresponding to region active material in, thus the uniformity of embedding lithium and embedding lithium efficiency
It is difficult to be guaranteed simultaneously.Secondly as embedding lithium total amount is few needed for pre-embedding lithium technique, and require accurately to control lithium-inserting amount,
This results in and uses metal lithium sheet to be difficult to meet accurate control amount requirement as the mode in lithium source.Finally, due to use, there is through hole
Collector can derive following problem: 1. active electrode material becomes increasingly difficult in the technique that supports of collector；2. restrict
The conductive capability of collector, the simultaneously contact resistance between increase active material and collector, thus the merit to lithium-ion capacitor
Rate characteristic has a negative impact；3. active material also can be affected in the caking property having on through hole collector, affect lithium from
The cycle life of sub-capacitor and reliability；4. increasingly complex owing to having the preparation technology of through hole collector, thus also can increase
Add the preparation cost of lithium-ion capacitor.
(Publication No. CN103021675A, publication date is on April 3rd, 2013 to patent of invention, and publication is entitled
" lithium-ion capacitor and cathode pole piece preparation method thereof ") and document " Development and characterization of
Li-ion capacitor pouch cells " in (Journal of Power Sources 257 (2014) 388-393),
Use lithium metal powder (or inerting lithium powder) to be directly coated on negative pole, realize to negative electrode active material when lithium-ion capacitor fluid injection
The pre-embedding lithium of matter.
In said method, lithium metal directly contacts with negative pole, can reduce the pre-embedding lithium time, it is also possible to avoid having through hole collection
The use of fluid.But, such method yet suffers from following defect: first, such method need after coating metallic lithium powder into
Row rolling, owing to metallic lithium powder quality is softer, ductility strong, after rolling, metallic lithium powder dense can be covered in embedding lithium activity material
On material, when hindering fluid injection, the infiltration of electrolyte anticathode pole piece, affects pre-embedding lithium effect, even affects lithium-ion capacitor
Energy；Second, the coated weight of lithium metal is the most less needed for lithium-ion capacitor negative pole, thus the more difficult control of coated weight, coating
Uniformity is difficult to be protected equally, and then affects the uniformity of pre-embedding lithium, also can affect the uniformity of lithium-ion capacitor；The
Three, the pre-process of intercalation of the method is after assembling, fluid injection, thus before lithium-ion capacitor assembles, its negative pole is still in lithium
Powder coating state, thus in an assembling process, easily causing metallic lithium powder comes off, and becomes and causes lithium ion during using from now on
The potential safety hazard of capacitor internal short-circuit；4th, owing to the pre-process of intercalation of direct contact type is equivalent to lithium metal and lithium ion
Capacitor anode carry out concentration of electrolyte in direct short-circuit, and pre-process of intercalation higher (for realize lithium-ion capacitor times
Rate characteristic, concentration of electrolyte can not reduce), thus embedding lithium speed is difficult to control, and there is potential safety hazard.
Summary of the invention
For technical problem present in prior art, an object of the present invention be to provide one can improve lithium from
The pre-embedding lithium method of the pre-embedding lithium efficiency of sub-capacitor cathode pole piece.
The technical solution adopted for the present invention to solve the technical problems is: the pre-embedding lithium side of a kind of lithium-ion capacitor negative pole
Method, carries out the most embedding lithium as lithium source to lithium-ion capacitor negative pole using lithium metal, comprises the steps:
S10, preparation has can embedding lithium active material layer and the cathode pole piece of current collector layers；
S20, in the moisture atmosphere less than 2 ‰, particle diameter is distributed D99 be not more than the metallic lithium powder of 200 μm with
The lithium salts non-protic organic solvent of 0.1 1M uniformly mixes, and is configured to mixed serum；
S30, dries cathode pole piece described in S10, and in the moisture atmosphere less than 2 ‰, will mix described in S20
Slurries even application at least one times, in cathode pole piece, stands 10min 24h after spraying every time；
S40, vacuum drying or dry in S30 under nitrogen or argon sprays, stand after cathode pole piece.
As preferably, the cathode pole piece in step S10 be first by embedding lithium active material negative material with conductive agent, bonding
Agent and solvent are mixed and made into active material slurry, then are coated in conductive current collector by above-mentioned slurry, after drying, rolling
Arrive.
As preferably, the cathode pole piece in step S10 is first by embedding lithium active material negative material and conductive agent, binding agent
And solvent mixing, then by material rolling film forming after mixing, finally become for rolling electrode film is compound on collector after rolling
Obtain.
As preferably, the embedding lithium active material in step S10 is for can embedding lithium material with carbon element or can embedding lithium metal oxide or lead
Electric polymer and compound thereof.
As preferably, described conductive agent is conductive black or electrically conductive graphite, and described binding agent is Kynoar, gathers
Tetrafluoroethene, butadiene-styrene rubber or sodium cellulose glycolate, described solvent is 1-METHYLPYRROLIDONE, deionized water or ethanol.
As preferably, the metallic lithium powder in step S20 is cladding Li2CO3Surface passivation lithium powder.
As preferably, in the mixed serum in step S20, metallic lithium powder percentage by weight is 10 30%.
As preferably, the lithium salts in step S20 is can be inorganic lithium salt or organic lithium salt, and described inorganic lithium salt is hexafluoro
Lithium phosphate, LiBF4, lithium perchlorate or hexafluoroarsenate lithium, described organic lithium salt is boryl class lithium salts, sulphonic acids lithium salts
Or imines lithium salts, described aprotic organic solvent is ethylene carbonate, propene carbonate, gamma butyrolactone, sulfolane, tetrahydrochysene
Furans, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, dimethoxy-ethane or acetonitrile.
As preferably, the ar gas environment less than 2% of the atmosphere oxygen content in step S30.
As preferably, during the standing in described step S30, use the standing of cathode pole piece encapsulation after described spraying
Mode.
As preferably, in step S30 in mixed serum spraying process, the mixed serum of configuration in step S20 is carried out even
Continuous property stirring, to improve the uniformity of mixed serum in spraying process.
As preferably, also include the step using the cathode pole piece prepared in aprotic organic solvent rinsing step S30.
The two of the purpose of the present invention are to provide the spray equipment of the pre-embedding lithium of a kind of lithium-ion capacitor negative pole.
The technical solution adopted for the present invention to solve the technical problems is: the pre-embedding lithium of a kind of lithium-ion capacitor negative pole
Spray equipment, including conveyer belt, control cabinet, the serum storage tank of storage metallic lithium powder mixed serum and by pulp-inlet pipe and slurries
Store up tank connected airless spraying system, described airless spraying system with include that control cabinet is connected, described slurries
The protective gas control valve and pressure sensor being connected with control cabinet, described airless spraying system it is respectively arranged with on storage tank
On system, connection has high-pressure hose, described conveyer belt to be driven by belt-driven axle, and belt-driven axle connects conveyer belt
Driving motor, belt-driven motor connects electric machine controller, and electric machine controller passes through control signal wire and control cabinet phase
Even, being provided with shower nozzle by shower nozzle slide bar support arm and move slide bar above conveyer belt, described shower nozzle moves and is provided with on slide bar
The controller for motor being connected with control cabinet, described controller for motor is provided with shower nozzle and drives motor, and shower nozzle drives horse
Reach and be provided with the spraying nozzle being connected with high-pressure hose.
As preferably, it is also equipped with agitating device in described serum storage tank, described spraying nozzle is provided with and controls
The shower nozzle displacement transducer that case processed connects, described conveyer belt is provided with the conveyer belt displacement transducer being connected with control cabinet.
The invention has the beneficial effects as follows:
The present invention uses the embedding lithium of mode that metallic lithium powder and electrolyte mixed serum are sprayed at cathode pole piece, it is achieved lithium metal source
Support the integral process with Lithium-ion embeding, simplify technological process, it is to avoid support the rolling process behind lithium source, lithium metal
Between particle, conduction liquid and negative pole embedding lithium active layer three, more preferably, embedding lithium speed is higher in contact.
The present invention uses spraying method to support lithium source in cathode pole piece, and the method is by moving with shower nozzle spray rate
The control of speed, it is achieved that to lithium source loading and the accurate control of spraying uniformity, improve the uniformity of the pre-embedding lithium of negative pole,
Ensure that the uniformity of lithium-ion capacitor, it is also possible to reduce the internal short-circuit potential safety hazard of lithium-ion capacitor, promote pre-embedding lithium
The security of technique.
The present invention realizes pre-embedding lithium before lithium-ion capacitor assembles, without free lithium powder when negative plate assembles, it is possible to reduce
Lithium-ion capacitor internal short-circuit risk during follow-up use.
It is dense that the present invention mixes lithium powder content and electrolyte in suspension by the spray rate and control controlling mixed serum
The mode of degree controls embedding lithium speed, thus promotes the security of embedding lithium technique.
Accompanying drawing explanation
Fig. 1 is the schematic flow sheet of the inventive method；
Fig. 2 is the structural representation of spray equipment used by the present invention；
Fig. 3 is the spraying path schematic diagram of the inventive method.
Each reference is: 1 serum storage tank, 2 agitating devices, 3 protective gas control valves, 4 pressure sensors,
5 pulp-inlet pipes, 6 airless spraying systems, 7 high-pressure hoses, 8 spraying nozzles, 9 shower nozzles drive motor, 10 horses
Reaching control device, 11 shower nozzle displacement transducers, 12 shower nozzles move slide bar, 13 shower nozzle slide bar support arms, 14 conveyer belts,
15 belt-driven axles, 16 conveyer belt displacement transducers, 17 belt-driven motors, 18 electric machine controllers, 19
Control cabinet, 20 negative plates.
Detailed description of the invention
Below in conjunction with the accompanying drawings the present invention is described in further detail.
Fig. 1 gives in lithium-ion capacitor preparation process, the flow chart of the pre-embedding lithium method of negative pole.To have porous
Carbon Materials is positive active material, with can the intercalation materials of li ions mixing as negative electrode active material, with organic lithium salt solution as electrolyte
In ultracapacitor preparation process, as lithium source, lithium-ion capacitor negative pole is carried out the most embedding lithium using lithium metal, mainly include
Below scheme:
S10, preparation has can embedding lithium active material layer and the lithium-ion capacitor cathode pole piece of current collector layers.The system of cathode pole piece
Preparation Method is conventional method prepared by this area electrode plates, can be found in following method: 1. by embedding lithium active material negative material
It is mixed and made into active material slurry with conductive agent, binding agent and solvent, above-mentioned slurry is coated in conductive current collector, through drying
Cathode pole piece is obtained after dry, rolling；2. or by embedding lithium active material negative material mix with conductive agent, binding agent and solvent, will
Material rolling film forming after mixing, then become for rolling electrode film is compound on collector obtain after rolling cathode pole piece.
S10, can embedding lithium active material can be can embedding lithium material with carbon element or can embedding lithium metal oxide or lead described in flow process
Electric polymer and compound thereof, as native graphite, Delanium, coke, carbonaceous mesophase spherules, hard charcoal, Graphene etc. can embedding lithiums
Material with carbon element or tin oxide, lithium titanate, titanium dioxide etc. can in the conducting polymer such as embedding lithium metal oxide or coalescence benzene at least
A kind of.Described conductive agent is the conductive agents such as conductive black commonly used in the art, electrically conductive graphite；Described binding agent is in this area
The binding agents such as conventional Kynoar, polytetrafluoroethylene (PTFE), butadiene-styrene rubber, sodium cellulose glycolate；Described solvent is this area
In conventional 1-METHYLPYRROLIDONE, deionized water, ethanol equal solvent.In actual applications, described active material, conductive agent,
Binding agent, the kind of solvent, each component ratio, the parameter such as the compacted density of pole piece and surface density, all can select as required
Select and design.
S20, in the moisture atmosphere less than 2 ‰, is distributed particle diameter D99 and is not more than the metallic lithium powder of 200 μm
Uniformly mix with the lithium salts non-protic organic solvent of 0.1 1M, be configured to mixed serum.Described lithium salts is for can have non-proton
Machine solvent dissolves all electrolyte lithium salts generating lithium ion.Can be inorganic lithium salt or organic lithium salt.Inorganic lithium salt such as hexafluoro
Lithium phosphate (LiPF6), LiBF4 (LiBF4), lithium perchlorate (LiClO4) or hexafluoroarsenate lithium (LiAsF6).Organic lithium salt
There is boryl class lithium salts such as di-oxalate lithium borate (LiB (C2O4)2) or LiODFB (LiBF2(C2O4)), sulphonic acids lithium salts
Such as trifluoromethyl sulfonic acid lithium (LiCF3SO3), alkyls lithium salts such as three (trimethyl fluoride sulfonyl) lithium methide (LiC (SO2CF3)3), sub-
Amine lithium salts such as double (fluorosulfonyl) imine lithium (LiN (SO2F)2) or double (trimethyl fluoride sulfonyl) imine lithium (LiN (SO2CF3)2),
Containing perfluor phosphine class such as three (pentafluoroethyl group) three lithium fluophosphate (LiPF3(C2F5)3) etc..Described aprotic organic solvent can be carbonic acid
Vinyl acetate (EC), propene carbonate (PC), gamma butyrolactone (γ-GBL), sulfolane (TMS), oxolane (THF), carbonic acid diformazan
Ester (DMC), diethyl carbonate (DEC), methyl ethyl carbonate (EMC), dimethoxy-ethane (DME) or acetonitrile (AN) etc..
S30, cathode pole piece described in baking step S10, and in the moisture atmosphere less than 2 ‰, by step
The even application at least one times of mixed serum described in S20, in cathode pole piece, stands 10min 24h after spraying every time.Standing
Cheng Zhong, the metallic lithium powder in mixed serum contacts with negative electrode active material, and molten with the organic lithium salt with ion conductivity
Liquid constitutes micro-electrochemical system, so that lithium metallic particles dissolves and is embedded in negative active core-shell material.
S40, vacuum drying or under nitrogen or argon baking step S30 spray, stand after cathode pole piece.
Comparing the pre-embedding lithium technology of existing lithium-ion capacitor negative pole, the lithium source that present invention achieves negative pole supports and lithium ion
The integral process embedded, simplifies pre-embedding lithium technique, improves pre-embedding lithium efficiency, and the method is prone to accurately control the load in lithium source
Carrying capacity and spraying uniformity, improve the uniformity of the pre-embedding lithium of negative pole, also improve the security of the pre-embedding lithium technique of negative pole simultaneously
Security with lithium-ion capacitor.
It is emphasized that the present invention provides only a kind of pre-embedding lithium method of lithium-ion capacitor negative pole, existing to solve
Relevant issues in pre-embedding lithium technology, concrete lithium-inserting amount will setting according to the characteristic of negative active core-shell material and lithium-ion capacitor
Depending on meter requires.
Fig. 2 gives spray equipment scheme schematic diagram (this figure only spraying of the pre-embedding lithium method of lithium-ion capacitor negative pole
The scheme schematic diagram of device, in order to illustrate embodiments of the present invention, it is impossible to represents actually used spray equipment completely, actual
The spray equipment used is also not necessarily limited to device shown in schematic diagram).
Metallic lithium powder mixed serum is stored in serum storage tank 1, pressure sensor 4 monitor tank inner pressure, by protecting
Protect gas control valve 3 and control protective gas air inflow to maintain tank inner pressure.Wherein protective gas is dry air or inertia
Gas.The mixed serum storage tank of spray equipment can choose to install agitating device 2, is used for carrying out it in spraying or slurries storing process
Stirring, to keep the uniformity of mixed serum.
Metallic lithium powder mixed serum sucks airless spraying system 6 through pulp-inlet pipe 4, through high-pressure hose 7 after pressurization, finally
Being sprayed by spraying nozzle, moment is atomized and is attached to negative plate 20 surface.Wherein the airless spraying decorum 6 can also use other
Spray equipment substitutes, such as compressed gas atomizer spray device or electrostatic atomization spray equipment, according to compressed gas atomizing spraying
Device, compressed gas used should be dry air or inert gas.
In spraying process, pole piece is positioned on conveyer belt 14, and conveyer belt is driven operating by belt-driven motor 17, by
Motion conditions monitored by conveyer belt displacement transducer 16, and controlled conveyer belt control motor 17 to adjust biography by electric machine controller 18
Send start and stop and the running speed of band, thus realize control pole piece sprayed in X-direction.Spraying nozzle 8 is fixed on shower nozzle motor 9
On, nozzle position sensor 11 and shower nozzle motor control device 10 shower nozzle motor movement on shower nozzle slide bar is monitored and controlled
Situation, thus realize the control in the Y direction pole piece sprayed.
Fluid reservoir gas shield valve 3, pressure sensor 4, airless spraying system 6, nozzle position sensor 11, shower nozzle
Motor control device 10, conveyer belt displacement transducer 16 are connected with control cabinet 19 by control signal wire with electric machine controller 18.Control
Pressure condition in case processed monitoring fluid reservoir 1, the spraying rate of monitoring high pressure painting system 6, and shower nozzle can be monitored at cathode pole piece
Spraying position on 20 and translational speed, thus coordinate to control the coordination operation of whole paint finishing, thus meet the spray of pre-embedding lithium
It is coated with requirement.
Fig. 3 gives spraying nozzle spraying path schematic diagram on negative plate 20, and (concrete spraying method is not limited to
This).During spraying, control cabinet 19 first controls shower nozzle driving motor 9 in y-axis direction with spraying rate v(m/s) at the uniform velocity spray,
When reaching to preset spraying terminal, control cabinet 19 sends instruction and suspends high pressure painting system 6 and shower nozzle driving motor 9, and starts
Belt-driven motor 17, makes cathode pole piece 20 position move l to x-axis direction1M () spacing distance, suspends after moving and passes
Sending band to drive motor 17, start high pressure painting system 6 simultaneously and shower nozzle drives motor 9, anticathode sheet 20 carries out y-axis opposite direction spray
Being coated with, when reaching to preset spraying terminal, control cabinet 19 sends instruction time-out high pressure painting system 6 and shower nozzle drives motor 9, and opens
Dynamic belt-driven motor 17, makes cathode pole piece 20 position move l again to x-axis direction1M () spacing distance, i.e. completes a spray
The painting cycle.So it is repeatedly completed the once spraying to whole cathode pole piece.
Assuming that the metallic lithium powder percentage composition of mixed serum is α (%), serum density is ρ (kg/L), airless spraying system
The spraying rate of system is V(L/s), whole pole piece once sprays and needs m spray cycles altogether, can be calculated pre-embedding by below equation
The quantity for spray in lithium lithium metal source:
The lithium metal source quantity for spray once sprayed is:(kg)；
The lithium metal source quantity for spray of M spraying is:(kg).
The method can be passed through accurately to control the spray rate of mixed serum and shower nozzle in cathode pole piece x and the spray in y direction
It is coated with the parameter such as position and spraying rate, accurately controls the lithium metal source quantity for spray to lithium-ion capacitor cathode pole piece.Additionally,
By controlling the uniformity of shower nozzle translational speed, control the uniformity of shower nozzle spraying rate, and ensure to spray spacing distance L1With
The modes such as the spray range diameter of shower nozzle is suitable, it is ensured that the uniformity of spraying.Uniform in the accuracy and spraying controlling quantity for spray
On the basis of property, i.e. can ensure that the uniformity of the pre-lithium-inserting amount of lithium-ion capacitor negative pole, thus improve lithium-ion capacitor
Uniformity.
Embodiment 1
S10, is mixed and made into active material slurry by artificial graphite material with conductive agent, binding agent and solvent, is coated with by above-mentioned slurry
It is overlying in conductive current collector, after drying, rolling, obtains cathode pole piece.
S20, in the water content atmosphere less than 2000ppm, using D50 is 90 μm, and D99 is not more than the gold of 150 μm
Belong to lithium powder, with the LiPF of 1M6/ EC+DEC(EC and DEC volume ratio is 1:1) solution mixes, and being made into metallic lithium powder content is 50%
Mixed serum.
S30, dries in S10 after made cathode pole piece, in the water content environment less than 2000ppm, uses spray equipment
Mixed serum configured in S20 is uniformly sprayed on above-mentioned drying cathode pole piece, stand 60min and realize pre-embedding lithium, the most instead
Multiple spraying altogether, stand 6 times after realize the embedding lithium of negative pole.Then use the cathode pole piece after the spraying of DEC eluent solvent, standing, clean
The LiPF introduced in step S206Electrolyte.
S40, under nitrogen protection, dries prepared cathode pole piece in S30 in 80 DEG C, completes pre-process of intercalation.
Embodiment 2
S10, mixes natural graphite material with conductive agent, binding agent and solvent, material rolling film forming after mixing, then by rolling
Become electrode film is compound on collector after rolling, then drying obtains cathode pole piece.
S20, is respectively less than in 1500ppm atmosphere in water, oxygen content, and using D50 is 20 μm, and D99 is not more than 35 μm
Metallic lithium powder, with the LiBF of 0.1M4/ EC+DMC(EC and DMC mass ratio is 1:2) solution mixes, and being made into metallic lithium powder content is
The mixed serum of 10%.
S30, dries in S10 after made cathode pole piece, in the water content environment less than 1500ppm, uses spray equipment
Mixed serum configured in S20 is uniformly sprayed on above-mentioned drying cathode pole piece, after standing 5h, the most repeatedly spray, stand 4
The embedding lithium of negative pole is realized after secondary.
S40, in 100 DEG C of vacuum drying S30, prepared cathode pole piece, completes pre-process of intercalation.
Embodiment 3
S10, is mixed and made into active material slurry by lithium titanate with conductive agent, binding agent and solvent, is coated on by above-mentioned slurry and leads
On electrojet body, after drying, rolling, obtain cathode pole piece.
S20, in the water content atmosphere less than 1000ppm, using D50 is 30 μm, and D99 is not more than the metal of 50 μm
Lithium powder, with the LiClO of 0.6M4/ PC+EMC(PC and EMC volume ratio is 1:1) solution mixes, and being made into metallic lithium powder content is 40%
Mixed serum.
S30, dries in S10 after made cathode pole piece, at water content less than 800ppm, the oxygen content environment less than 1.5%
In, use spray equipment uniformly to spray on above-mentioned drying cathode pole piece by mixed serum configured in S20, stand 6h and realize negative
The most embedding lithium.
S40, under argon shield, dries prepared cathode pole piece in S30 in 150 DEG C, completes pre-process of intercalation.
Embodiment 4
S10, mixes natural hard carbon material with conductive agent, binding agent and solvent, material rolling film forming after mixing, then by rolling
Become electrode film is compound on collector after rolling, then drying obtains cathode pole piece.
S20, in water content is 500ppm atmosphere, using D50 is 50 μm, and D99 is not more than the metallic lithium powder of 80 μm,
LiAsF with 0.3M6/ DMC solution mixes, and is made into the mixed serum that metallic lithium powder content is 40%.
S30, dries in S10 after made cathode pole piece, and in the water content environment less than 500ppm, employing spray equipment will
In S20, configured mixed serum uniformly sprays and (opens agitating device in spraying process, in stirring on above-mentioned drying cathode pole piece
State the mixed serum of metallic lithium powder and lithium salt electrolyte), stand 3h after spraying and realize the embedding lithium of negative pole.
S40, under argon shield, dries prepared cathode pole piece in S30 in 110 DEG C, completes pre-process of intercalation.
Embodiment 5
S10, is mixed and made into active material slurry by MCMB with conductive agent, binding agent and solvent, is coated with by above-mentioned slurry
It is overlying in conductive current collector, after drying, rolling, obtains cathode pole piece.
S20, in water content is less than 100ppm atmosphere, using D50 is 150 μm, and D99 is not more than the metal of 200 μm
Lithium powder, with the LiB (C of 0.4M2O4)2/ AN(solution mixes, and is made into the mixed serum that metallic lithium powder content is 5%.
S30, dries in S10 after made cathode pole piece, at water content less than 100ppm, the oxygen content argon gas gas less than 1%
In atmosphere environment, spray equipment is used uniformly to spray on above-mentioned drying cathode pole piece by mixed serum prepared in S20, after spraying
Stand 10h and realize the embedding lithium of negative pole.
S40,60 DEG C of vacuum is dried prepared cathode pole piece in S30, is completed pre-process of intercalation.
Embodiment 6
S10, is mixed and made into active material slurry by soft charcoal material with conductive agent, binding agent and solvent, is coated on by above-mentioned slurry
In conductive current collector, after drying, rolling, obtain cathode pole piece.
S20, in water content is 50ppm atmosphere, using D50 is 10 μm, and D99 is not more than the metallic lithium powder of 15 μm,
LiN (SO with 0.2M2CF3)2/ DMC solution mixes, and is made into the mixed serum that metallic lithium powder content is 60%.
S30, dries in S10 after made cathode pole piece, and in the water content environment less than 50ppm, employing spray equipment will
In S20, configured mixed serum uniformly sprays on above-mentioned drying cathode pole piece, uses aluminum plastic film encapsulation above-mentioned after spraying
Pole piece, then stand 24h and realize the embedding lithium of negative pole.
S40, in 70 DEG C of vacuum drying S30, prepared cathode pole piece, completes pre-process of intercalation.
Embodiment 7
S10, is mixed and made into active material slurry, by above-mentioned by Delanium, grapheme material with conductive agent, binding agent and solvent
Slurry is coated in conductive current collector, obtains cathode pole piece after drying, rolling.
S20, in water content is 2000ppm atmosphere, using D50 is 5 μm, and D99 is not more than the cladding of 7.5 μm
Li2CO3Surface passivation metallic lithium powder, with the LiCF of 0.9M3SO3The volume ratio of/PC+EMC(PC and EMC is 1:1) solution mixes
Close, be made into the mixed serum that metallic lithium powder content is 70%.
S30, dries in S10 after made cathode pole piece, in the water content environment less than 2000ppm, uses spray equipment
Mixed serum configured in S20 is uniformly sprayed on above-mentioned drying cathode pole piece, stand 10min after spraying, the most repeatedly spray
Be coated with, standing realizes the embedding lithium of negative pole for 10 times.
S40, in 100 DEG C of vacuum drying S30, prepared cathode pole piece, completes pre-process of intercalation.
Embodiment 8
S10, is mixed and made into active material slurry by titanium dioxide with conductive agent, binding agent and solvent, is coated on by above-mentioned slurry
In conductive current collector, after drying, rolling, obtain cathode pole piece.
S20, in water content is less than 1800ppm atmosphere, using D50 is 80 μm, and D99 is not more than the metal of 115 μm
Lithium powder, with the LiBF of 0.6M2(C2O4The volume ratio of)/PC+EC+EMC(PC, EC and EMC is 1:1:3) solution mixing, it is made into metal
Lithium powder content is the mixed serum of 25%.
S30, dries in S10 after made cathode pole piece, at water content less than 50ppm, the oxygen content gas less than 100ppm
In atmosphere environment, spray equipment is used uniformly to spray on above-mentioned drying cathode pole piece (spray coated by mixed serum configured in S20
Journey is opened agitating device, stirs the mixed serum of above-mentioned metallic lithium powder and lithium salt electrolyte), stand 20h after spraying and realize negative
The most embedding lithium.
S40, under nitrogen protection, dries prepared cathode pole piece in S30 in 90 DEG C, completes pre-process of intercalation.
Embodiment 9
S10, is mixed and made into active material slurry by Si-C composite material with conductive agent, binding agent and solvent, is coated with by above-mentioned slurry
It is overlying in conductive current collector, after drying, rolling, obtains cathode pole piece.
S20, in water content is less than 5ppm atmosphere, using D50 is 170 μm, and D99 is not more than the lithium metal of 200 μm
Powder, with the LiN (SO of 0.5M2F)2/ PC solution mixes, and is made into the mixed serum that metallic lithium powder content is 30%.
S30, dries in S10 after made cathode pole piece, and in the water content environment less than 2ppm, employing spray equipment will
In S20, configured mixed serum uniformly sprays and (opens agitating device in spraying process, in stirring on above-mentioned drying cathode pole piece
State the mixed serum of metallic lithium powder and lithium salt electrolyte), stand 15h after spraying and realize pre-embedding lithium.Then PC eluent solvent is used
Cathode pole piece after spraying, standing, the electric LiN (SO introduced in cleaning step S202F)2Xie Zhi.
S40, under argon shield, dries prepared cathode pole piece in S30 in 170 DEG C, completes pre-process of intercalation.
Embodiment 10
S10, is mixed and made into active material slurry by hard carbon material with conductive agent, binding agent and solvent, is coated on by above-mentioned slurry
In conductive current collector, after drying, rolling, obtain cathode pole piece.
S20, is respectively less than in 2000ppm atmosphere in water, oxygen content, and using D50 is 100 μm, and D99 is not more than 115 μm
Metallic lithium powder, with the LiC (SO of 0.8M2CF3)3/ THF solution mixes, and is made into the mixed serum that metallic lithium powder content is 45%.
S30, dries in S10 after made cathode pole piece, in the environment of 100ppm, uses spray equipment will to be joined in S20
Put mixed serum uniformly to spray on above-mentioned drying cathode pole piece and (spraying process to be opened agitating device, stirs above-mentioned lithium metal
Powder and the mixed serum of lithium salt electrolyte), use aluminum plastic film to encapsulate above-mentioned pole piece after spraying, it is embedding that standing 18h realizes negative pole
Lithium.Then take aluminum plastic film apart and take out pole piece, use the cathode pole piece after the spraying of THF eluent solvent, standing, in cleaning step S20
LiC (the SO introduced2CF3)3Electrolyte.
S40, in 50 DEG C of vacuum drying S30, prepared cathode pole piece, completes pre-process of intercalation.
Embodiment 11
S10, mixes natural hard charcoal, the same conductive agent of grapheme material, binding agent and solvent, material rolling film forming after mixing,
Again become for rolling electrode film is compound on collector after rolling, then drying obtains cathode pole piece.
S20, in water content is 2000ppm atmosphere, using D50 is 50 μm, and D99 is not more than the cladding of 99 μm
Li2CO3Surface passivation metallic lithium powder, with the LiPF of 0.3M3(C2F5)3/ TMS solution mixes, and being made into metallic lithium powder content is 30%
Mixed serum.
S30, dries in S10 after made cathode pole piece, in the water content environment less than 1500ppm, uses spray equipment
Mixed serum configured in S20 is uniformly sprayed and (in cathode pole piece spraying process is opened agitating device, stirs above-mentioned lithium metal
Powder and the mixed serum of lithium salt electrolyte), stand 8h after spraying and realize the embedding lithium of negative pole.
S40, under argon shield, dries prepared cathode pole piece in S30 in 160 DEG C, completes pre-process of intercalation.
The principle of above-described embodiment only illustrative present invention and effect thereof, and the embodiment that part is used, for
For those of ordinary skill in the art, without departing from the concept of the premise of the invention, it is also possible to make some deformation and
Improving, these broadly fall into protection scope of the present invention.
Claims (14)
1. the pre-embedding lithium method of a lithium-ion capacitor negative pole, it is characterised in that comprise the steps:
S10, preparation has can embedding lithium active material layer and the cathode pole piece of current collector layers；
S20, in the moisture atmosphere less than 2 ‰, particle diameter is distributed D99 be not more than the metallic lithium powder of 200 μm with
The lithium salts non-protic organic solvent of 0.1 1M uniformly mixes, and is configured to mixed serum；
S30, dries cathode pole piece described in S10, and in the moisture atmosphere less than 2 ‰, will mix described in S20
Slurries even application at least one times, in cathode pole piece, stands 10min 24h after spraying every time；
S40, vacuum drying or dry in S30 under nitrogen or argon sprays, stand after cathode pole piece.
The pre-embedding lithium method of a kind of lithium-ion capacitor negative pole the most according to claim 1, it is characterised in that described step
Cathode pole piece in S10 is first by embedding lithium active material negative material and to be mixed and made into activity with conductive agent, binding agent and solvent
Compound paste, more above-mentioned slurry is coated in conductive current collector, obtain after drying, rolling.
The pre-embedding lithium method of a kind of lithium-ion capacitor negative pole the most according to claim 1, it is characterised in that described step
Cathode pole piece in S10 is first to be mixed with conductive agent, binding agent and solvent by embedding lithium active material negative material, then by after mixing
Material rolling film forming, finally is compound to obtain on collector by become for rolling electrode film after rolling.
The pre-embedding lithium method of a kind of lithium-ion capacitor negative pole the most according to claim 1, it is characterised in that described step
Embedding lithium active material in S10 is can embedding lithium material with carbon element or can embedding lithium metal oxide or conducting polymer and compound thereof.
5. according to the pre-embedding lithium method of a kind of lithium-ion capacitor negative pole described in Claims 2 or 3, it is characterised in that described
Conductive agent be conductive black or electrically conductive graphite, described binding agent is Kynoar, polytetrafluoroethylene (PTFE), butadiene-styrene rubber or hydroxyl
Sodium carboxymethylcellulose pyce, described solvent is 1-METHYLPYRROLIDONE, deionized water or ethanol.
The pre-embedding lithium method of a kind of lithium-ion capacitor negative pole the most according to claim 1, it is characterised in that described step
Metallic lithium powder in S20 is cladding Li2CO3Surface passivation lithium powder.
The pre-embedding lithium method of a kind of lithium-ion capacitor negative pole the most according to claim 1, it is characterised in that described step
In mixed serum in S20, metallic lithium powder percentage by weight is 10 30%.
The pre-embedding lithium method of a kind of lithium-ion capacitor negative pole the most according to claim 1, it is characterised in that described step
Lithium salts in S20 is can be inorganic lithium salt or organic lithium salt, and described inorganic lithium salt is lithium hexafluoro phosphate, LiBF4, height
Lithium chlorate or hexafluoroarsenate lithium, described organic lithium salt is boryl class lithium salts, sulphonic acids lithium salts or imines lithium salts, and described is non-
Proton-organic solvent is ethylene carbonate, propene carbonate, gamma butyrolactone, sulfolane, oxolane, dimethyl carbonate, carbonic acid
Diethylester, methyl ethyl carbonate, dimethoxy-ethane or acetonitrile.
The pre-embedding lithium method of a kind of lithium-ion capacitor negative pole the most according to claim 1, it is characterised in that described step
The atmosphere oxygen content in the S30 ar gas environment less than 2%.
The pre-embedding lithium method of a kind of lithium-ion capacitor negative pole the most according to claim 1, it is characterised in that described step
During standing in rapid S30, use the standing mode of cathode pole piece encapsulation after described spraying.
The pre-embedding lithium method of 11. a kind of lithium-ion capacitor negative poles according to claim 1, it is characterised in that described step
In rapid S30 in mixed serum spraying process, the mixed serum of configuration in step S20 is carried out continuous stirring.
The pre-embedding lithium method of 12. a kind of lithium-ion capacitor negative poles according to claim 1, it is characterised in that also include
Use the step of the cathode pole piece prepared in aprotic organic solvent rinsing step S30.
The spray equipment of the pre-embedding lithium of 13. 1 kinds of lithium-ion capacitor negative poles as claimed in claim 1, it is characterised in that: include
Conveyer belt (14), control cabinet (19), storage metallic lithium powder mixed serum serum storage tank (1) and by pulp-inlet pipe (5) with slurry
The airless spraying system (6) that liquid storage tank (1) connects, described airless spraying system (6) with include control cabinet (19)
Connect, described serum storage tank (1) is respectively arranged with the protective gas control valve (3) being connected with control cabinet (19) and pressure passes
Sensor S40, the upper connection of described airless spraying system (6) has high-pressure hose (7), and described conveyer belt (14) is by conveyer belt
Drive shaft (15) drives, and the upper connection of belt-driven axle (15) has belt-driven motor (17), belt-driven motor (17)
Upper connection has electric machine controller (18), and electric machine controller (18) is connected with control cabinet (19) by control signal wire, conveyer belt
(14) top is provided with shower nozzle by shower nozzle slide bar support arm (13) and moves slide bar (12), and described shower nozzle moves on slide bar (12)
It is provided with the controller for motor (10) being connected with control cabinet (19), described controller for motor (10) is provided with shower nozzle and drives
Dynamic motor (9), shower nozzle drives and is provided with, on motor (9), the spraying nozzle (8) being connected with high-pressure hose (7).
The pre-embedding lithium method of 14. a kind of lithium-ion capacitor negative poles according to claim 13, it is characterised in that described
It is also equipped with agitating device (2) in serum storage tank (1), described spraying nozzle (8) is provided with and is connected with control cabinet (19)
Shower nozzle displacement transducer (11), described conveyer belt (14) is provided with the conveyer belt displacement transducer being connected with control cabinet (19)
(16).
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